Catalytic composition and its preparation and use for preparing polymers from ethylenically unsaturated monomers

ABSTRACT

A catalytic composition, including a cationic metal-pair complex, is disclosed, along with a method for its preparation. A method for the polymerization of ethylenically unsaturated monomers using the catalytic composition, and the addition polymers produced thereby are also disclosed.

This patent application derives priority from U.S. patent applicationSer. No. 60/579,311, filed Jun. 14, 2004.

The present invention relates to a catalytic composition and a method ofpreparing that catalytic composition. The present invention furtherrelates to a method for polymerizing ethylenically unsaturated monomers,including non-polar olefinic monomers, polar olefinic monomers, andcombinations thereof, in the presence of the catalytic composition, andto the polymers produced thereby.

Both poly(non-polar)olefins and polyacrylates find their origins in the1930's. At their inception, both families of polymers were made usingfree radical chemistry, and seventy years later acrylic polymerscontinue to be made predominately using free radical chemistry carriedout predominately in batch mode. Ethylene polymerization, on the otherhand, has enjoyed a number of breakthroughs so that today thepreponderance of polyethylene produced (>80%) is prepared by continuousprocesses using transition metal catalysts. The use of transition metalcatalysts has significantly improved economics (low energy, low pressureprocesses), greatly improved product properties (e.g., the strength ofultra-thin plastic bags), resulted in new products (new grades ofpolyethylene, elastomers, medical packaging) and even brand new polymers(e.g., polypropylene) by virtue of the molecular level control ofpolymer architecture endowed by these catalysts.

The evolution of olefin polymerization catalysis since Karl Ziegler'sNobel Prize-winning discovery of the transition metal catalyzedpolymerization of ethylene in 1953 has involved a prolific coupling ofpolymer science with organometallic chemistry. Successes include thedevelopment of catalysts that rival the activities of enzymes, and ofsystems that yield polyolefins with controlled molecular weights andtacticities. In stark contrast, despite nearly 50 years of intenseactivity and progress spurred on by the predicted enormous profitsassociated with the new commercial products that would becomeaccessible, there are no commercially viable catalysts for thepolymerization of acrylates or the controlled copolymerization of simpleolefins with polar functional monomers.

Currently, commercial processes for the copolymerization of ethylenewith polar monomers such as acrylates, methacrylates, and vinyl acetateemploy free radical processes in which the incorporation of the polarfunctionality is relatively random. The use of free radical initiatorsacross the entire acrylic polymer market gives little or no control overpolymer architecture (tacticity or crystallinity, blockiness, molecularweight, and molecular weight distribution) and thus limits theaccessible range of materials performance properties. Because these freeradical processes require extreme pressures, they are associated withhigh capital investment and manufacturing costs, and, of course,increased safety hazards.

Industry-wide, a need exists for new molecular catalysts capable ofpolymerizing polar monomers in a controlled fashion and forcopolymerizing the same monomers with olefins (e.g. ethylene, propylene,styrene, octene, norbornene) under mild reaction conditions and in astereoregular (“tactic”) fashion. Of the many approaches to modifyingthe properties of a polymer that are available, the incorporation offunctional groups into an otherwise non-polar material is of paramountimportance. Polar groups exercise control over important polymerproperties such as toughness, adhesion, barrier properties, and surfaceproperties. These polymer properties, manifest themselves in theproperties of materials incorporating the polymer, such as solventresistance, miscibility with other polymers, and rheological properties,leading to product performance such as paintability, printability,gloss, hardness, and mar resistance. By incorporating polar groups intohydrocarbon polymers such as polyethylene, polypropylene andpolystyrene, not only would the important properties related tocrystallinity (modulus, strength, solvent resistance, etc.) bemaintained, but new properties would also be expressed.

In recent years, late transition metal catalysts have attractedattention not only for the polymerization of α-olefins, but moreimportantly for the copolymerization of hydrocarbon monomers withreadily available polar monomers such as acrylates and vinyl acetate.Only very recently have these single metal centered catalysts providedthe very first examples of the transition-metal catalyzed incorporationof acrylate monomers into linear polyethylene been demonstrated.Unfortunately, all of these reports describe catalysts with poorperformance; low productivity, low molecular weight copolymers and lowlevels of polar monomer incorporation.

The total focus on single metal centered catalysts is apparent frommyriad papers and reviews of the area. For example, Rolf Muelhaupt in“Catalytic Polymerization and Post Polymerization Catalysis Fifty YearsAfter the Discovery of Ziegler's Catalysts”, Macromol. Chem. Phys. 2003,204, 289–327 elegantly and comprehensively reviews fifty years ofdevelopments and again we highlight that exclusively single metal ormonometallic catalysts are described and reviewed—regardless of whetherthe catalysts are based on early transition metals such as titanium orzirconium, or late transition metals such as nickel and palladium, orwhether the catalysts were studied in the 1950's, 60's, 70's, 80's, 90'sor the present day. FIGS. 12 and 13 on page 298 of the Muelhauptreference (vide supra) clearly summarize this concentration on singlemetal centers rather than the metal atom pair containing complexes ofthe present invention.

U.S. Pat. No. 6,303,724 discloses the use of specific monometalliccationic Pd complexes to polymerize mixtures of norbornene and acrylatemonomers to make norbornene/acrylate compositions. Unfortunately, themethod of U.S. Pat. No. 6,303,724 produces mixtures, the copolymercontent of which is low (see Comparative Examples herein), so low, infact, that these mixtures of polymers are ineffectual in uses for whicha pure copolymer could be employed with advantageous result. In fact, inthe presence of both norbornene and acrylate monomers, thosemonometallic cationic Pd complexes give only homopolymers of norbornenewith no acrylate incorporation or, at most, homopolymers having a singleacrylate monomer incorporated as an end group.

We have surprisingly discovered a catalytic composition including a newfamily of cationic metal-pair complexes which are very active in thehomo- and co-polymerization of ethylenically unsaturated monomers. Theethylenically unsaturated monomers polymerizable by catalysis using thecatalytic composition of the present invention include non-polarolefinic monomers, polar olefinic monomers, and combinations thereof.This new family of catalytic compositions includes cationic metal-paircomplexes wherein the cationic metal-pair complex includes at least onemetal atom pair, and one metal of the metal atom pair has five (5)occupied coordination sites and the other metal of the metal atom pairhas four(4), five (5), or six (6) occupied coordination sites.

One aspect of the present invention is directed to a catalyticcomposition comprising at least one cationic metal-pair complex,wherein:

-   said cationic metal-pair complex comprises at least one metal atom    pair, said pair comprising a first metal atom, M¹, and a second    metal atom, M²;-   said first metal atom and said second metal atom of said pair have a    through-space internuclear distance of at least 1.5 Angstroms and no    more than 20 Angstroms; and-   said cationic metal-pair complex is a complex according to formula    I,

wherein:

-   M¹ represents a first metal atom selected from iron, cobalt,    ruthenium, rhodium, chromium, and manganese;-   L¹ represents a set of first ligands;-   L² represents a set of second ligands;-   L³ represents a set of third ligands;-   R¹ represents a set of first anionic hydrocarbyl containing    radicals;-   R² represents a set of second anionic hydrocarbyl containing    radicals;-   S¹ represents a set of first labile ligands;-   S² represents a set of second labile ligands;-   A¹–A³ each represent a set of coordination bonds;-   WCA represents a weakly coordinating anion;-   a, b, h, k, m, and p are each selected from 0 and 1;-   α, β, and c each equal 1;-   d, r, and t are each selected from 0, 1, 2, 3, and 4;-   f is selected from 1, 2, 3, 4, and 5;-   l≦m+p≦2;-   the sum d+f+r+t=5; and-   sum e+g+s+u=4, 5, or 6; and-   wherein:-   when the sum e+g+s+u=4,-   M² represents a second metal atom selected from nickel, palladium,    copper, iron, cobalt, rhodium, chromium, and manganese;-   e, s, and u are each selected from 0, 1, 2, and 3;-   g is selected from 1, 2, 3, and 4;-   0≦d+e≦6; 1≦r+s≦6; 0≦t+u≦6;and 2≦f+g≦8;-   when the sum e+g+s+u=5,-   M² represents a second metal atom selected from iron, cobalt,    ruthenium, rhodium, chromium, and manganese;-   e, s, and u are each selected from 0, 1, 2, 3, and 4;-   g is selected from 1, 2, 3, 4, and 5;-   0≦d+e≦7; 1≦r+s≦7; 0≦t+u≦7; and 2≦f+g≦9; or-   when the sum e+g+s+u=6,-   M² represents a second metal atom selected from copper, iron,    cobalt, ruthenium, rhodium, chromium, and manganese;-   e, s, and u are each selected from 0, 1, 2, 3, 4, and 5;-   g is selected from 1, 2, 3, 4, 5, and 6;-   0≦d+e≦8; 1≦r+s≦8; 0≦t+u≦8; and 2≦f+g≦10.

A second aspect of the present invention is directed to a method forpreparing a catalytic composition, comprising:

-   providing a full-(metal pair) precursor complex according to said    formula II

wherein:

-   M¹ represents a first metal atom selected from iron, cobalt,    ruthenium, rhodium, chromium, and manganese;-   L¹ represents a set of first ligands;-   L² represents a set of second ligands;-   L³ represents a set of third ligands;-   R¹ represents a set of first anionic hydrocarbyl containing    radicals;-   R² represents a set of second anionic hydrocarbyl containing    radicals;-   S¹ represents a set of first labile ligands;-   S² represents a set of second labile ligands;-   A¹–A¹⁰ each represents a set of coordination bonds;-   WCA represents a weakly coordinating anion;-   Y represents a leaving group;-   d+f+r+t+x=5; and-   the sum e+g+s+u+y=4, 5, or 6;-   combining said full-(metal pair) precursor complex with at least one    activator component;-   removing said leaving group Y from said full-(metal pair) precursor    complex; and-   replacing said leaving group Y with at least one replacement moiety;-   wherein for said full-(metal pair) precursor complex-   α, β, and c each equal 1;-   a, b, h, k, m, p, x, and y are each selected from 0 and 1;-   d, r, and t are each selected from 0, 1, 2, 3, and 4;-   f is selected from 1, 2, 3, 4, and 5;-   1≦m+p≦2; and-   1≦x+y≦2; and-   wherein:-   when the sum e+g+s5+u+y=4,-   M² represents a second metal atom selected from nickel, palladium,    copper, iron, cobalt, rhodium, chromium, and manganese;-   e, s, and u are selected from 0, 1, 2, and 3;-   g is selected from 1, 2, 3, and 4;-   0≦d+e≦5; 1≦r+s≦6; 0≦t+u≦5; and 2≦f+g≦7;-   when the sum e+g+s+u+y=5,-   M² represents a second metal atom selected from iron, cobalt,    ruthenium, rhodium, chromium, and manganese;-   e, s, and u are selected from 0, 1, 2, 3, and 4;-   g is selected from 1, 2, 3, 4, and 5;-   0≦d+e≦6; 1≦r+s≦7; 0≦t+u≦6; and 2≦f+g≦8; or-   when the sum e+g+s+u+y=6,-   M² represents a second metal atom selected from copper, iron,    cobalt, ruthenium, rhodium, chromium, and manganese;-   e, s, and u are each selected from 0, 1, 2, 3, 4, and 5;-   g is selected from 1, 2, 3, 4, 5, and 6;-   0≦d+e≦7; 1≦r+s≦8; 0≦t+u≦7; and 2≦f+g≦9.

A third aspect of the present invention is directed to a method forpreparing a catalytic composition, comprising:

-   providing a first semi-(metal pair) precursor complex and a second    semi-(metal pair) precursor complex both according to formula II

wherein:

-   -   M¹ represents a first metal atom selected from iron, cobalt,        ruthernium, rhodium, chromium, and manganese;    -   L¹ represents a set of first ligands;    -   L² represents a set of second ligands;    -   L³ represents a set of third ligands;    -   R¹ represents a set of first anionic hydrocarbyl containing        radicals;    -   R² represents a set of second anionic hydrocarbyl containing        radicals;    -   S¹ represents a set of first labile ligands;    -   S² represents a set of second labile ligands;    -   A¹–A¹⁰ each represents a set of coordination bonds;    -   WCA represents a weakly coordinating anion; and    -   Y represents a leaving group;

-   (ii) combining said first semi-(metal pair) precursor complex with    at least one activator component;

-   (iii) removing said leaving group Y from said first semi-(metal    pair) precursor complex; and

-   (iv) replacing said leaving group Y with said second semi-(metal    pair) precursor complex;

-   wherein for said first semi-(metal pair) precursor complex    -   α and x each equal 1;    -   β, b, c, k, p, e, f, g, s, u, and y each equal 0;    -   a, h, and m are each selected from 0 and 1;    -   d, r, and t are each selected from 0, 1, 2, 3, and 4; and    -   the sum d+f+r+t+x=5; and

-   wherein for said second semi-(metal pair) precursor complex    -   β equals 1;    -   α, a, c, h, m, d, f, g, r, t, x, and y each equal 0;    -   b, k, and p are each selected from 0 and 1; and    -   the sum e+g++u+y=4, 5 and 6; and

-   wherein:    -   when the sum e+g+s+u+y=4,        -   M² represents a second metal atom selected from nickel,            palladium, copper, iron, cobalt, rhodium, chromium, and            manganese;        -   e is selected from 0, 1, 2, 3, and 4; and        -   s and u are each selected from 0, 1, 2, and 3;        -   when the sum e+g+s+u+y=5,        -   M² represents a second metal atom selected from iron,            cobalt, ruthenium, rhodium, chromium, and manganese;        -   e is selected from 0, 1, 2, 3, 4, and 5; and        -   s and u are each selected from 0, 1, 2, 3, and 4; or    -   when the sum e+g+s+u+y=6        -   M² represents a second metal atom selected from copper,            iron; cobalt, ruthenium, rhodium, chromium, and manganese;        -   e is selected from 0, 1, 2, 3, 4, 5, and 6; and        -   s and u are each selected from 0, 1, 2, 3, 4, and 5; and

-   wherein the sum of m of said first semi-(metal pair) precursor    complex+p of said second semi-(metal pair) precursor complex is    selected from 1 or 2.

A fourth aspect of the present invention is directed to a method forpreparing a catalytic composition, comprising:

-   (i) providing a first semi-(metal pair) precursor complex and a    second semi-(metal pair) precursor complex both according to formula    II

-   wherein:    -   M¹ represents a first metal atom selected from iron, cobalt,        ruthenium, rhodium, chromium, and manganese;    -   L¹ represents a set of first ligands;    -   L² represents a set of second ligands;    -   L³ represents a set of third ligands;    -   R¹ represents a set of first anionic hydrocarbyl containing        radicals;    -   R² represents a set of second anionic hydrocarbyl containing        radicals;    -   S¹ represents a set of first labile ligands;    -   S² represents a set of second labile ligands;    -   A¹–A¹⁰ each represents a set of coordination bonds;    -   WCA represents a weakly coordinating anion; and    -   Y represents a leaving group;-   (ii) combining said first semi-(metal pair) precursor complex with    at least one activator component;-   (iii) removing said leaving group Y from said first semi-(metal    pair) precursor complex; and-   (iv) replacing said leaving group Y with said second semi-(metal    pair) precursor complex; wherein for said first semi-(metal pair)    precursor complex    -   β and y each equal 1;    -   α, a, c, h, m, d, f, g, r, t, and x each equal 0;    -   b, k, and p are each selected from 0 and 1; and    -   the sum e+g+s+u+y=4, 5 or 6; and        wherein:    -   when the sum e+g+s+u+y=4,        -   M² represents a second metal atom selected from nickel,            palladium, copper, iron, cobalt, rhodium, chromium, and            manganese; and        -   e, s and u are each selected from 0, 1, 2, and 3;    -   when the sum e+g+s+u+y=5,        -   M² represents a second metal atom selected from iron,            cobalt, ruthenium, rhodium, chromium, and manganese; and        -   e, s and u are each selected from 0, 1, 2, 3, and 4; or        -   when the sum e+g+s+u+y=6        -   M² represents a second metal atom selected from copper,            iron, cobalt, ruthenium, rhodium, chromium, and manganese;            and        -   e, s and u are each selected from 0, 1, 2, 3, 4, and 5; and-   wherein for said second semi-(metal pair) precursor complex    -   α equals 1;    -   β, b, c, k, p, e, f, g, s, u, x, and y each equal 0;    -   a, h, and m are each selected from 0 and 1;    -   d is selected from 0, 1, 2, 3, 4, and 5;    -   r and t are each selected from 0, 1, 2, 3, and 4; and    -   the sum d+f+r+t+x=5; and-   wherein the sum of m of said first semi-(metal pair) precursor    complex+p of said second semi-(metal pair) precursor complex is    selected from 1 or 2.

A still further aspect of the present invention is directed to a methodfor preparing at least one addition polymer comprising:

-   (a) combining:    -   (i) a catalytic composition according the first aspect of the        present invention; and    -   (ii) at least one ethylenically unsaturated monomer; and-   (b) polymerizing said at least one ethylenically unsaturated monomer    in the presence of said catalytic composition to form said addition    polymer.

Used herein, the following terms have these definitions:

“Range”. Disclosures of ranges herein take the form of lower and upperlimits. There may be one or more lower limits and, independently, one ormore upper limits. A given range is defined by selecting one lower limitand one upper limit. The selected lower and upper limits then define theboundaries of that particular range. All ranges that can be defined inthis way are inclusive and combinable, meaning that any lower limit maybe combined with any upper limit to delineate a range.

A “catalytic composition” is a composition including at least one“cationic metal-pair complex”, wherein the cationic metal-pair complexincludes at least one “metal atom pair”. Each metal atom pair includes asingle “first metal atom” represented by the symbol “M¹” (“metal atomM¹”) and a single “second metal atom” represented by the symbol “M²”(“metal atom M²”).

The “through-space internuclear metal atom pair distance” (referred tointerchangeably, herein, as “through-space internuclear distance”) for ametal atom pair of a cationic metal-pair complex is the distance betweenthe nucleus of the first metal atom M¹ of a metal atom pair and thenucleus of the second metal atom M² of that pair. This through-spaceinternuclear distance is equal to or less than the “through-bondinternuclear distance”, which is the distance traced along connectingbonds. For example, if a metal-metal bond exists between M¹ and M² of ametal atom pair, the through-space internuclear distance and themetal-metal through-bond distance are the same. If this metal atom pairalso had a third ligand as a bridging moiety between M¹ and M², thedistance from M¹ to M² along the bonds of that third ligand would begreater than the through-space distance.

The “through-space internuclear metal atom pair distance” for a metalpair of a cationic metal-pair complex may be determined using quantumchemical calculation methods known to those of ordinary skill in the artof computational chemistry. For example, a quantum chemical calculationmethod suitable for use with the present invention includes densityfunctional methods such as JAGUAR™ software, Version 5.0. For a givencationic metal-pair complex, one of ordinary skill in the art ofcomputational chemistry can utilize accepted rules of chemicalconnectivity, the “LACVP basis set”, and the “B3LYP functional” tocalculate the interatomic metal-metal distance (i.e., the through-spaceinternuclear metal atom pair distance) for a metal pair of that cationicmetal-pair complex. Using JAGUAR™ software, Version 5.0, the structureof the cationic metal-pair complex is geometry optimized, using as astarting point a structure having the proper atomic connectivity. Themetal-metal interatomic distance for a metal pair of that complex (i.e.,the “through-space internuclear metal pair distance”) can then bedetermined from the atomic Cartesian coordinates of the geometryoptimized structure. JAGUAR™ software, Version 5.0. and the Jaguar 5.0Operating Manual, January 2003, are available from Schrödinger, L. L.C., 120 West 45^(th) Street, 32^(nd) Floor, New York, N.Y. 10036.

The first metal atom and the second metal atom of a metal atom pair mayfurther exhibit “cooperativity” during the polymerization ofethylenically unsaturated monomers, wherein cooperativity means that thefirst metal atom will positively influence the ability of the secondmetal atom to polymerize ethylenically unsaturated monomer, or thesecond metal atom will positively influence the ability of the firstmetal atom to polymerize ethylenically unsaturated monomer, or both.Such embodiments, therefore include a polymerization system includingthe catalytic composition of the present invention and at least oneethylenically unsaturated monomer, wherein the first metal atom and thesecond metal atom exhibit cooperativity during catalysis of thepolymerization of ethylenically unsaturated monomers. Not wishing to bebound by any particular theory, it is thought that, when the two metalsof a metal atom pair exhibit cooperativity, that cooperativity may, forexample, take the form wherein a metal of the pair favorably modifiesthe electronic, steric, or other spatial environment of the other metalof the pair, or of the inserting ethylenically unsaturated monomer, orof the portion of any polymer chain growing from, or otherwiseassociated with, the metal atom pair. In certain embodiments, a singleethylenically unsaturated monomer may become attached to, or otherwiseassociated with, each of the members of a metal atom pair, eithersequentially or simultaneously, during its incorporation into a polymerby insertion polymerization catalyzed by that metal atom pair.

A “coordination bond” can be a bond between a “coordination site” of afirst metal atom, M¹, and any one of the following: first ligand;bridging moiety; first anionic hydrocarbyl radical; first labile ligand;or metal atom M². A “coordination bond” can also be a bond between a“coordination site” of a second metal atom, M², and any one of thefollowing: second ligand; bridging moiety; second anionic hydrocarbylradical; second labile ligand; or metal atom M¹. A set of coordinationbonds is represented by the symbol “A”, having a superscript denotingthe position of that bond in the “cationic metal-pair complex formula”(vide infra) and a subscript denoting the number of coordination bonds.

The term “ligand” has its usual meaning in organometallic chemistry. A“ligand” is a moiety bearing one or more “donor sites”, wherein a “donorsite” is an electron rich site (e.g., lone electron pair) capable offorming a “coordination bond” with a metal atom by donating electrondensity to an unoccupied (i.e., electron deficient) “coordination site”on that metal atom. The ligand is said to be “occupying thatcoordination site” on that metal atom. Alternatively, the ligand is saidto be “coordinately bound” to the metal atom. When one or morecoordination bonds exist between a ligand and a metal atom, both thatligand and that metal atom are said to be “participating” in each ofthose coordination bonds.

A “neutral electron donor ligand” is any ligand which, when removed froma metal atom (i.e., one or more coordination bonds are broken) in itsclosed shell electron configuration, has a neutral charge. For example,triphenylphosphine is a neutral electron donor ligand.

A “monodentate ligand” is a ligand bearing a single “donor site”. Forexample, triphenylphosphine is a monodentate ligand, the phosphorus loneelectron pair of which is a donor site capable of coordinating to (i.e.,occupying a coordination site of) a metal atom.

A “bidentate ligand” is a ligand bearing two donor sites. For example,1,2-bis(diphenylphosphino)ethane is a bidentate ligand. Each of the twodonor sites of a bidentate ligand may be able to form a coordinationbond to the same metal atom. Alternatively, one donor site of abidentate ligand may form a coordination bond to one metal atom, whilethe other donor site of the same bidentate ligand may form acoordination bond to a different metal atom.

A “multi-dentate ligand” bears two or more donor sites, each of which iscapable of coordinating to a metal atom. For example,pentamethyldiethylenetriamine is a multi-dentate ligand having threesuch donor sites. Provided that such considerations as steric andelectronic factors allow it, each of the donor sites of a multi-dentateligand may be able to form a coordination bond to the same metal atom.Alternatively, at least one donor site of a multi-dentate ligand mayform a coordination bond to one metal atom, while at least one otherdonor site of the same multi-dentate ligand may form a coordination bondto a different metal atom, and each of those two metal atom could be inthe same metal-atom pair, or in two different metal-atom pairs of thecomplex that contains one or more metal-atom pairs. A “bidentate ligand”is a special case of a “multi-dentate ligand”.

It is further possible that fewer than all of the donor sites of aligand may actually participate in coordination bonds. Therefore, forany ligand, the “effective number of donor sites” of that ligand isequal to the number of donor sites actually participating incoordination bonds. It follows that an “effectively monodentate ligand”is a ligand having a total of one donor site participating in acoordination bond. Similarly, for example, “effectively bidentate”,“effectively tridentate”, “effectively tetradentate”, “effectivelypentadentate”, and “effectively hexadentate” ligands have, respectively,two, three, four, five, and six donor sites participating incoordination bonds. As a further example, pentamethyldiethylenetriaminehas three amine lone electron pairs as donor sites, and is therefore atridentate ligand. If only two of the amine lone electron pairs of thistriamine were participating in coordination bonds with one metal, or twometals of a metal atom pair, the triamine would be effectively bidentatewith respect to that metal atom pair. If only one of those electronpairs were participating in a coordination bond with a metal, thetriamine would be effectively monodentate. As a further example, theallyl anion is effectively monodentate in its η¹-allyl form, buteffectively bidentate in its η³-allyl form.

A “first ligand” may be any ligand capable of participating in one ormore coordination bonds with metal atom M¹ of a metal atom pair, whilenot simultaneously participating in a coordination bond with metal atomM² of that same metal atom pair.

A “second ligand” may be any ligand capable of participating in one ormore coordination bonds with metal atom M² of a metal atom pair, whilenot simultaneously participating in a coordination bond with metal atomM¹ of that same metal atom pair.

A “third ligand” of the present invention may be any ligand capable ofparticipating, simultaneously, in at least one coordination bond witheach of metal atom M¹ and metal atom M², of the same metal atom pair.The terms “third ligand” and “bridging moiety” are used interchangeablyherein.

A “labile neutral electron donor ligand” is any neutral electron donorligand which is not strongly bound to a metal atom (e.g., M¹ or M²), andis easily displaced therefrom. The terms “labile neutral electron donorligand” and “labile ligand” are used interchangeably herein.

A “first labile ligand” is a labile ligand capable of participating in acoordination bond with metal atom M¹, while not simultaneouslyparticipating in a coordination bond with metal atom M².

A “second labile ligand” is a labile ligand capable of participating ina coordination bond with metal atom M², while not simultaneouslyparticipating in a coordination bond with metal atom M¹.

An anionic ligand, is any ligand which, when removed from a metal atom(e.g., M¹ or M²) in its closed shell electron configuration, has anegative charge.

A “multi-(metal pair) coupling moiety”, referred to herein,interchangeably, as a “pair-coupling moiety” is any multi-dentate moietycapable of participating, simultaneously, in at least one coordinationbond with each of at least two metal atom pairs of a single complex. A“pair-coupling moiety” includes multiple donor sites having constraints(for example, steric constraints, electronic constraints, or both)allowing one or more of those donor sites to participate in coordinationbonds with one metal pair while, simultaneously, one or more of itsother donor sites is participating in coordination bonds with anothermetal pair. Though not wishing to be bound by any particular theory, itis believed that the number of metal pairs that can simultaneouslyparticipate in one or more coordination bonds with the samepair-coupling moiety is governed by such considerations as, for example:steric constraints of the pair-coupling moiety; electronic constraintsof the donor sites of the pair-coupling moiety; electronic and spatialcharacteristics of metal atoms M¹ and M² within and, where there aremultiple metal-atom pairs in the same complex, between metal atom pairs;steric and electronic characteristics of any other first ligand, secondligand, bridging moiety, first anionic hydrocarbyl containing radical,second anionic hydrocarbyl containing radical, first labile ligand,second labile ligand, or leaving group that is simultaneouslyparticipating in a coordination bond, or bonds, with either metal atomM¹ or M² of each metal atom pair; the mole ratios of the pair-couplingmoiety to the metal pairs; and the accessibility of donor sites (e.g., apair-coupling moiety may be a porous polymeric structure, wherein somedonor sites may be inaccessible to metal atom pairs). Further, themaximum number of metal atom pairs that may possibly be coordinatelybound to a single pair-coupling moiety is equal to the number of donorsites on that pair-coupling moiety. However, one or more of theconstraints listed supra may intervene to limit the number of metal atompairs that are actually bound to a single pair-coupling moiety to anumber less than that maximum value. It may also be the case that asingle pair-coupling moiety may participate in multiple coordinationbonds with one or both of metal atoms M¹ and M² of a single metal pair.There is no particular limit on the size of the pair-coupling moiety.For example, the pair-coupling moiety may be a macroreticular resinbearing donor sites (vide infra), a crown ether, or othermacro-structure bearing multiple donor sites.

A “pair-coupling moiety” is a moiety capable of participating incoordination bonds with two or more metal atom pairs of a complex of thepresent invention, provided, of course, that the complex has at leasttwo metal atom pairs and that constraints such as those just enumeratedallow coordination bonds to multiple metal atom pairs. The followingcomplexes of the present invention may contain one or more pair-couplingmoieties: cationic metal-pair complex; and precursor complexes,including full-(metal pair) precursor complex; first semi-(metal pair)precursor complex; and second semi-(metal pair) precursor complex. Whentwo or more metal atom pairs are present in a complex of the presentinvention: all of metal atoms M¹ may be identical (e.g., all might beNi); all of metal atoms M² may be identical; metal atom M¹ may differfrom pair to pair (e.g., one might be Ni, while another would be Pd);and metal atom M² may differ from pair to pair. In the case of first andsecond semi-(metal pair) complexes, either metal atom M¹ or M², but notboth, will be present in each pair of the semi-(metal pair) complex. A“pair-coupling moiety” may be any of the following: first ligand, secondligand, third ligand, first labile ligand, second labile ligand, firsthydrocarbyl radical, second hydrocarbyl radical, or combinationsthereof.

A “weakly coordinating anion” (“WCA”) is an anion which is only weaklyassociated with the cationic metal-pair complex. The WCA is sufficientlylabile to be displaced by a neutral Lewis base, solvent or monomer. Morespecifically, the WCA functions as a stabilizing anion to the cationicmetal-pair complex and does not transfer sufficient electron density tothe cationic metal-pair complex to form a neutral product. The WCA isrelatively inert in that it is non-oxidative, non-reducing, andnon-nucleophilic.

A “cationic metal-pair complex” is a complex represented by thefollowing “cationic metal-pair complex formula” (“formula I”):

and the following symbols and subscripts have these meanings in thecationic metal-pair complex formula:

The symbols “M¹” and “M²” represent, respectively, a first metal atom ofa metal atom pair and a second metal atom of a metal atom pair. Thecationic metal-pair formula subscript “α” on the symbol “M¹ _(α)”,indicates whether metal atom M¹ is present in (α=1) or absent from (α=0)a metal atom pair of a cationic metal-pair complex. The cationicmetal-pair formula subscript “β” on the symbol “M² _(β)”, indicateswhether metal atom M² is present in (β=1) or absent from (β=0) a metalatom pair of a cationic metal-pair complex. Because both of metal atomsM¹ and M² must be present in any metal atom pair of a cationicmetal-pair complex, the following relationship exists: α=β=1.

The symbol “L¹” represents a “set of first ligands”, wherein a “firstligand” is a ligand coordinately bound to metal atom M¹, but notcoordinately bound to metal atom M². This set of first ligands may,interchangeably, be referred to as “set L¹”. The cationic metalpair-complex formula subscript “a”, of “L¹ _(a)”, equals either theinteger 0 or 1. When “a”=1, set L¹ includes one or more first ligands.When “a”=0, set L¹ is “empty”. When a ligand set is empty, that ligandset contains no ligands. For example, when “a”=0, set L¹ contains nofirst ligands.

The symbol “L²” represents a “set of second ligands”, wherein a “secondligand” is a ligand coordinately bound to metal atom M², but notcoordinately bound to metal atom M¹. This set of second ligands may,interchangeably, be referred to as “set L²”. The cationic metalpair-complex formula subscript “b”, of “L² _(b)”, equals either 0 or 1.When “b”=1, set L² includes one or more second ligands. When “b”=0, setL²is empty.

The symbol “L³” represents a “set of bridging moieties”. A “bridgingmoiety” is a moiety coordinately bound to both metal atom M¹ and metalatom M² of the same metal atom pair. A metal-metal bond is a specialcase of a bridging moiety wherein the moiety is the bond itself, andinvolves no other atoms beyond the two metal atoms of the metal-metalbond. This set of bridging moieties may, interchangeably, be referred toas “set L³”. The cationic metal pair-complex formula subscript “c”, of“L³ _(c)”, equals 1 in the cationic metal-pair complex formula,indicating that set L³ includes one or more bridging moieties. The terms“bridging moiety” and “third ligand” are used interchangeably herein.Bridging moieties include any multi-dentate ligand capable of beingsimultaneously coordinately bound to both metal atom M¹ and metal atomM². A crown ligand (e.g., “cationic metal-pair complex 1” infra) istherefore a bridging moiety and a member of set L³ if it issimultaneously coordinately bound to both metal atom M¹ and metal atomM². “Third labile ligands”, “third anionic hydrocarbyl containingradicals”, and “metal-metal bonds” between metal atom M¹ and metal atomM² of a metal atom pair are included in the definition of “third ligand”(“bridging moiety”).

The symbol “R¹” represents a “set of first anionic hydrocarbylcontaining radicals” coordinately bound to metal atom M¹, but not tometal atom M². This set of first anionic hydrocarbyl containing radicalsmay, interchangeably, be referred to as “set R¹”. Herein, the, term“first hydrocarbyl radical” is used interchangeably with the term “firstanionic hydrocarbyl containing radical”. The cationic metal pair-complexformula subscript “m”, of “R¹ _(m)”, equals either 0 or 1. When “m”=1,set R¹ includes one or more first hydrocarbyl radicals. When “m”=0, setR¹ is empty.

The symbol “R²” represents a “set of second anionic hydrocarbylcontaining radicals” coordinately bound to metal atom M², but not tometal atom M¹. This set of second anionic hydrocarbyl containingradicals may, interchangeably, be referred to as “set R²”. Herein, theterm “second hydrocarbyl radical” is used interchangeably with the term“second anionic hydrocarbyl containing radical”. The subscript “p”, of“R² _(p)”, equals either the integer 0 or 1. When subscript “p”=1, setR² includes one or more second hydrocarbyl radicals. When subscript“p”=0, set R² is empty. The relationship that, if one of the sets R¹ andR² is empty, then the other set must contain at least one hydrocarbylradical is represented by the following relationship: 1≦m+p≦2.

It is also possible for a hydrocarbyl radical to simultaneouslyparticipate in at least one coordination bond of each of first metalatom, M¹, and second metal atom, M², of the same metal atom pair. Thiscase is described herein as a “third anionic hydrocarbyl containingradical”, alternatively “third hydrocarbyl radical”. A “thirdhydrocarbyl radical” is a special case of a “bridging moiety”, L³.

An “anionic hydrocarbyl containing radical” (interchangeably,“hydrocarbyl radical”) is any hydrocarbyl radical which, when removedfrom a metal atom (e.g., M¹ or M²) in its closed shell electronconfiguration, has a negative charge. In any complex of the presentinvention in which they both are present, a first hydrocarbyl radicaland a second hydrocarbyl radical may be the same or different. When aset R¹ contains more than one first hydrocarbyl radical, those firsthydrocarbyl radicals may all be the same, or one or more may bedifferent from at least one other first hydrocarbyl radical of that setR¹. When a set R² contains more than one second hydrocarbyl radical,those second hydrocarbyl radicals may all be the same, or one or moremay be different from at least one other second hydrocarbyl radical ofthat set R².

The symbol “S¹” represents a “set of first labile ligands”, wherein a“first labile ligand” is a labile ligand coordinately bound to metalatom M¹, but not coordinately bound to metal atom M². This set of firstlabile ligands may, interchangeably, be referred to as “set S¹”. Thecationic metal pair-complex formula subscript “h”, of “S¹ _(h)”, equalseither 0 or 1. When “h”=1, set S¹ includes one or more first labileligands. When “h”=0, set S¹ is “empty”. When a labile ligand set isempty, that labile ligand set contains no ligands. For example, when“h”=0, set S¹ is empty. When set S¹ contains more than one first labileligand, those first labile ligands may all be the same, or one or moremay be different from at least one other first labile ligand of that setS¹.

The symbol “S²” represents a “set of second labile ligands”, wherein a“second labile ligand” is a labile ligand coordinately bound to metalatom M², but not coordinately bound to metal atom M¹. This set of secondlabile ligands may, interchangeably, be referred to as “set S²”. Thecationic metal pair-complex formula subscript “k”, of “S² _(k)”, equalseither 0 or 1. When “k”=1, set S² includes one or more second labileligands. When “k”=0, set S² is empty. When a set S² contains more thanone second labile ligand, those second labile ligands may be all be thesame, or one or more may be different from at least one other secondlabile ligand of that set S². In any cationic metal-pair complex of thepresent invention in which they both are present, a first labile ligandand a second labile ligand may be the same or different.

It is also possible for a labile ligand to simultaneously participate inat least one coordination bond of each of first metal atom, M¹, andsecond metal atom, M², of the same metal atom pair. This case isdescribed herein as a “third labile ligand”. A “third labile ligand” isa special case of a “bridging moiety”, L³.

The symbol “A¹” represents a set of coordination bonds between any firstligands of set L¹ and first metal atom, M¹ of a metal atom pair of thecationic metal-pair complex.

The symbol “A²” represents a set of coordination bonds between anysecond ligands of set L² and second metal atom, M² of a metal atom pairof the cationic metal-pair complex.

The symbol “A³” represents a set of coordination bonds between anybridging moieties of set L³ and first metal atom, M¹ of a metal atompair of the cationic metal-pair complex.

The symbol “A⁴” represents a set of coordination bonds between anybridging moieties of set L³ and second metal atom, M² of a metal atompair of the cationic metal-pair complex.

The symbol “A⁵” represents a set of coordination bonds between any firsthydrocarbyl radicals of set R¹ and first metal atom, M¹ of a metal atompair of the cationic metal-pair complex.

The symbol “A⁶” represents a set of coordination bonds between anysecond hydrocarbyl radicals of set R² and second metal atom, M² of ametal atom pair of the cationic metal-pair complex.

The symbol “A⁷” represents a set of coordination bonds between any firstlabile ligands of set S¹ and first metal atom, M¹ of a metal atom pairof the cationic metal-pair complex.

The symbol “A⁸” represents a set of coordination bonds between anysecond labile ligands of set S² and second metal atom M² of a metal atompair of the cationic metal-pair complex.

Any of the sets of coordination bonds represented by the symbol “A” may,interchangeably, be referred to as “set A”. For example, the set ofcoordination bonds represented by the symbol “A¹” may, interchangeably,be referred to as “set A¹”.

If any of sets L¹, L², R¹, R², S¹, and S² is empty, the cation formulasubscript of any symbol “A” representing any coordination bonds directlyassociated with that set will equal 0. For example, if set L¹ is empty,“a” of “L¹ _(a)” equals 0, and “d” of “A¹ _(d)”, also equals 0. Itfollows that, if any of cationic metal pair-complex formula subscripts“a”, “b”, “h”, “k”, “m”, and “p” equal 0, then the correspondingcationic metal pair-complex formula subscripts “d”, “e”, “t”, “u”, “r”,and “s” will, respectively, equal 0. These relationships also existamong the precursor formula subscripts of the “precursor complexformula” (vide infra).

If any of sets L¹, L², L³, R¹, R², S¹, and S² is occupied, i.e.,contains at least one member of its set, the cationic metal pair-complexformula subscript of any symbol “A”, representing any coordination bondsdirectly associated with a member of that set, will equal at least 1.That is, for any of sets L¹, L², L³, R¹, R², S¹, and S² that areoccupied, the corresponding cationic metal pair-complex formulasubscripts d, e, f, g, r, s, t, or u will, respectively, equal atleast 1. For example, if set L¹ of a “cationic metal-pair complex” isoccupied, “a” of “L¹ _(a)” equals 1, and “d” of “A¹ _(d)”, equals atleast 1. Further, if any of sets L¹, L², L³, R¹, R², S¹, and S² isoccupied, and the cationic metal pair-complex formula subscript of asymbol “A” representing coordination bonds directly associated with amember, or members, of that set equals at least 2, the pluralcoordination bonds indicated by that subscript may all emanate from asingle member of that set, or, alternatively, emanate from more than onemember of that set. For example, if “e”, of “A² _(e)”, equals theinteger 3, then set L² may contain one, two, or three second ligands. Inthis example, set L² may contain any of these combinations: threeeffectively monodentate second ligands (vide supra); one effectivelymonodentate second ligand and one effectively bidentate second ligand;or one effectively tridentate second ligand.

When a “metal-metal bond” exists between first metal atom, M¹, andsecond metal atom, M², of a metal atom pair of a cationic metal-paircomplex, the presence of that metal-metal bond is indicated in thecationic metal-pair complex formula by incrementing both of subscripts“f” and “g” by 1. In this specific case of a metal-metal bond, thecombination of an A³ bond and an A⁴ bond represents one single bondbecause there exist no atoms in the bridging moiety, that is, theelectron cloud of the bond between metal atom M¹ and metal atom M² isthe bridging moiety. This same formalism, wherein both subscripts “f”and “g” are incremented by 1 to indicate a metal-metal bond, holds whena metal-metal bond exists between a first metal atom, M¹, and a secondmetal atom, M², of a “precursor complex” of the present invention (i.e.,when the precursor complex is a fill-(metal pair) precursor complex).

The “cationic metal-pair complex formula subscripts” have values whichare either positive integers or zero. M¹ and M², and cationic metalpair-complex formula subscripts have these definitions: a, b, h, k, m,and p are selected from 0 or 1; α, β, and c each equal 1; d, r, and tare each selected from 0, 1, 2, 3, and 4; f is selected from 1, 2, 3, 4,and 5; 1≦m+p≦2; the sum d+f+r+t=5; and sum e+g+s+u=4 ,5, or 6; andwherein:

-   M¹ represents a first metal atom selected from iron, cobalt,    ruthenium, rhodium, chromium, and manganese; and-   when the sum e+g+s+u=4, M² represents a second metal atom selected    from nickel, palladium, copper, iron, cobalt, rhodium, chromium, and    manganese; e, s, and u are each selected from 0, 1, 2, and 3; g is    selected from 1, 2, 3, and 4; 0≦d+e≦6; 1≦r+s≦6; 0≦t+u≦6; and    2≦f+g≦8;-   when the sum e+g+s+u=5, M² represents a second metal atom selected    from iron, cobalt, ruthenium, rhodium, chromium, and manganese; e,    s, and u are each selected from 0, 1, 2, 3, and 4; g is selected    from 1, 2, 3, 4, and 5; 0≦d+e≦7; 1≦r+s≦7; 0≦t+u≦7;and 2≦f+g≦9; or-   when the sum e+g+s+u=6, M² represents a second metal atom selected    from copper, iron, cobalt, ruthenium, rhodium, chromium, and    manganese; e, s, and u are each selected from 0, 1, 2, 3, 4, and 5;    g is selected from 1, 2, 3, 4, 5, and 6; 0≦d+e≦8; 1≦r+s≦8; 0≦t+u≦8;    and 2≦f+g≦10.

A “precursor complex” is a complex according to the following “precursorcomplex formula” (“formula II”):

Symbols “M¹”, “M²”, “R¹”, “R²”, “L¹”, “L²”, “L³”, “S¹”, and “S²”, of the“precursor complex formula” have, respectively, the same meaning as thesymbols M¹, M², R¹, R², L¹, L², L³, S¹, and S² of the “cationicmetal-pair complex formula”.

Symbols “A¹”, “A²” “A³”, “A⁴”, “A⁵”, “A⁶”, “A⁷”, and “A⁸”, of the“precursor complex formula” have, respectively, the same meaning as thesymbols A¹, A², A³, A⁴, A⁵, A⁶, A⁷, and A⁸ of the “cationic metal-paircomplex formula”.

Although both M¹ and M² of the at least one metal atom pair of the“cationic metal-pair complex” are always present in the “cationicmetal-pair complex”, one member of the at least one metal atom pair ofthe “precursor complex” may be absent. For that reason precursor formulasubscripts “α” and “β” have, respectively been added to “M¹” and “M²” inthe “precursor complex formula”. The precursor formula subscript “α” onthe symbol “M¹ _(α)”, indicates whether metal atom M¹ is present in(α=1) or absent from (α=0) a metal atom pair of a precursor complex. Theprecursor formula subscript “β” on the symbol “M² _(β)”, indicateswhether metal atom M² is present in (β=1) or absent from (β=0) a metalatom pair of a precursor complex. Because either one or both of metalatoms M¹ and M² must be present in any metal atom pair of a precursorcomplex, the following relationship exists: 1≦α+β≦2. The “precursorcomplex subscripts” have values which are either positive integers orzero.

Symbol “Y” represents a leaving group of the precursor complex.

A “leaving group” is a moiety capable of being removed from theprecursor complex of the present invention by the action of an“activator component”.

Symbol “A⁹” represents a set of coordination bonds between leaving groupY and first metal atom, M¹ of a metal atom pair of a precursor complex.

Symbol “A¹⁰” represents a set of coordination bonds between leavinggroup Y and second metal atom, M of a metal atom pair of a precursorcomplex.

An “activator component” is a moiety capable of removing a leaving groupY from a “coordination site” of: metal atom M¹ of a precursor complex;metal atom M² of the precursor complex; or each of metal atom M¹ andmetal atom M² of the precursor complex.

A “full-(metal-pair) precursor complex” is a precursor complex accordingto the precursor complex formula (formula II) wherein M¹ represents afirst metal atom selected from iron, cobalt, ruthenium, rhodium,chromium, and manganese, and M² and the precursor formula subscriptshave these definitions: d+f+r+t+x=5; the sum e+g+s+u+y=4, 5, or 6; α, β,and c each equal 1; a, b, h, k, m, p, x, and y are each selected from 0and 1; d, r, and t are each selected from 0, 1, 2, 3, and 4; f isselected from 1, 2, 3, 4, and 5; 1≦m+p≦2; and 1≦x+y≦2; and wherein:

-   -   when the sum e+g+s+u+y=4,        -   M² represents a second metal atom selected from nickel,            palladium, copper, iron, cobalt, rhodium, chromium, and            manganese;        -   e, s, and u are selected from 0, 1, 2, and 3;        -   g is selected from 1, 2, 3, and 4;        -   0≦d+e≦5; 1≦r+s≦6; 0≦t+u≦5; and 2≦f+g≦7;    -   when the sum e+g+s+u+y=5,        -   M² represents a second metal atom selected from iron,            cobalt, ruthenium, rhodium, chromium, and manganese;        -   e, s, and u are selected from 0, 1, 2, 3, and 4;        -   g is selected from 1, 2, 3, 4, and 5;        -   0≦d+e≦6; 1≦r+s≦7; 0≦t+u≦6; and 2≦f+g≦8; or    -   when the sum e+g+s+u+y=6,        -   M² represents a second metal atom selected from copper,            iron, cobalt, ruthenium, rhodium, chromium, and manganese;        -   e, s, and u are each selected from 0, 1, 2, 3, 4, and 5;        -   g is selected from 1, 2, 3, 4, 5, and 6;        -   0≦d+e≦7; 1≦r+s≦8; 0≦t+u≦7; and 2≦f+g≦9.

A “first semi-(metal-pair) precursor complex” is a precursor complexaccording to the precursor complex formula (formula II) wherein M¹ andM², and the precursor formula subscripts have these definitions:

when α equals 1:

-   M¹ represents a first metal atom selected from iron, cobalt,    ruthernium, rhodium, chromium, and manganese;-   x equals 1; β, b, c, k, p, e, f, g, s, u, and y each equal 0; a, h,    and m are each selected from 0 and 1; and d, r, and t are each    selected from 0, 1, 2, 3, and 4; and d+f+r+t+x=5; and    when β equals 1;-   y equals 1; α, a, c, h, m, d, f, g, r, t, and x each equal 0; b, k,    and p are each selected from 0 and 1; and-   the sum e+g+s+u+y=4, 5 or 6; and-   wherein:    -   when the sum e+g+s+u+y=4,        -   M² represents a second metal atom selected from nickel,            palladium, copper, iron, cobalt, rhodium, chromium, and            manganese; and        -   e, s and u are each selected from 0, 1, 2, and 3;    -   when the sum e+g+s+u+y=5,        -   M² represents a second metal atom selected from iron,            cobalt, ruthenium, rhodium, chromium, and manganese; and        -   e, s and u are each selected from 0, 1, 2, 3, and 4; or    -   when the sum e+g+5+u+y=6        -   M² represents a second metal atom selected from copper,            iron, cobalt, ruthenium, rhodium, chromium, and manganese;            and        -   e, s and u are each selected from 0, 1, 2, 3, 4, and 5.

A “second semi-(metal-pair) precursor complex” is a precursor complexaccording to the precursor complex formula (formula II) wherein M¹ andM², and the precursor formula subscripts have these definitions:

when β equals 1:

-   α, a, c, h, m, d, f, g, r, t, x, and y each equal 0; b, k, and p are    each selected from 0 or 1; and the sum e+g+s+u+y=4, 5 or 6; and-   wherein:    -   when the sum e+g+s+u+y=4,        -   M² represents a second metal atom selected from nickel,            palladium, copper, iron, cobalt, rhodium, chromium, and            manganese;        -   e is selected from 0, 1, 2, 3, or 4; and        -   s and u are each selected from 0, 1, 2, or 3;    -   when the sum e+g+s+u+y=5,        -   M² represents a second metal atom selected from iron,            cobalt, ruthenium, rhodium, chromium, and manganese;        -   e is selected from 0, 1, 2, 3, 4, or 5; and        -   s and u are each selected from 0, 1, 2, 3, or 4; or    -   when the sum e+g+s+u+y=6        -   M² represents a second metal atom selected from copper,            iron, cobalt, ruthenium, rhodium, chromium, and manganese;        -   e is selected from 0, 1, 2, 3, 4, 5, or 6; and        -   s and u are each selected from 0, 1, 2, 3, 4, or 5; and            when α equals 1;-   M¹ represents a first metal atom selected from iron, cobalt,    ruthenium, rhodium, chromium, and manganese;-   β, b, c, k, p, e, f, g, s, u, x, and y each equal 0; a, h, and m are    each selected from 0 or 1; d is selected from 0, 1, 2, 3, 4, or 5; r    and t are each selected from 0, 1, 2, 3, or 4; and the sum    d+f+r+t+x=5.

When a first semi-(metal-pair) precursor complex and a secondsemi-(metal-pair) precursor complex are used to prepare a cationicmetal-pair complex in the method of preparation of the cationicmetal-pair complex of the present invention, that firstsemi-(metal-pair) precursor complex and that second semi-(metal-pair)precursor complex are related in the following ways:

-   the sum of “m” of said first semi-(metal pair) complex+“p” of said    second semi-(metal pair) complex is selected from 1 or 2;-   when α=x=1 for the first semi-(metal pair) complex, at least one    second ligand of the second semi-(metal pair) complex (β=1, y=0) has    at least one donor site available to fill a metal coordination site    vacated by the leaving group Y; and, similarly,-   when β=y=1 for the first semi-(metal pair) complex, at least one    first ligand of the second semi-(metal pair) complex (α=1, x=0) has    at least one donor site available to replace Y.

A “replacement moiety” is any moiety capable of becoming any of thefollowing: first ligand, second ligand, first hydrocarbyl-containingradical, second hydrocarbyl-containing radical, first labile ligand,second labile ligand, and bridging moiety. A “replacement moiety” iscapable of replacing a leaving group during or after removal of thatleaving group from a full-(metal pair) precursor comple or a firstsemi-(metal pair) precursor complex.

The term “ethylenically unsaturated monomer” refers to a molecule havingone or more carbon-carbon double bonds, and capable of insertionaddition polymerization. The term “monoethylenically unsaturatedmonomer” refers to an ethylenically unsaturated monomer having onecarbon-carbon double bond capable of insertion addition polymerization.The term “multiethylenically unsaturated monomer” refers to anethylenically unsaturated monomer having two or more carbon-carbondouble bonds capable of insertion addition polymerization.

The term “non-polar olefinic monomer” (alternatively “non-polar olefin”)refers to an ethylenically unsaturated monomer consisting exclusively ofhydrogen and carbon atoms. The non-polar olefinic monomers of thepresent invention are any non-polar olefinic monomers capable of beingpolymerized using the cationic metal-pair complex of the presentinvention to form “poly(non-polar olefin)s” or “poly[(polarolefin)-(non-polar olefin)]s”.

The term “polar olefinic monomer” (alternatively “polar olefin”) refersto an ethylenically unsaturated monomer including at least one atomother than carbon or hydrogen. The polar olefinic monomers of thepresent invention are any polar olefinic monomers capable of beingpolymerized using the cationic metal-pair complex of the presentinvention to form “poly(polar olefin)s” or “poly[(polarolefin)-(non-polar olefin)]s”.

The term “(meth)acryl” refers to both “acryl” and “methacryl”. Forexample, “butyl (meth)acrylate” refers to both “butyl acrylate” and“butyl methacrylate”. “(Meth)acryl” type monomers are examples of the“polar olefinic monomer” of the present invention.

An “addition polymer” is a polymer capable of being prepared by additionpolymerization, and selected from the group consisting of poly(non-polarolefin), poly(polar olefin), poly[(polar olefin)-(non-polar olefin)],and combinations thereof.

A “poly(non-polar olefin)” is a polymer comprising one or more non-polarolefinic monomers, as polymerized units. As such, a “poly(non-polarolefin)” may be a homopolymer or a copolymer, and the copolymer may be,for example, a random, alternating, or block copolymer.

A “poly(polar olefin)” is a polymer comprising, as polymerized units,one or more polar olefinic monomers. As such, a “poly(polar olefin)” maybe a homopolymer or a copolymer, and the copolymer may be, for example,a random, alternating, or block copolymer.

A “poly[(polar olefin)-(non-polar olefin)]” is a copolymer comprisingone or more non-polar olefinic monomers and one or more polar olefinicmonomers, as polymerized units, and the copolymer may be, for example, arandom, alternating, or block copolymer. The addition polymer of thepresent invention is a polymer selected from the group consisting of:poly(non-polar olefin), poly(polar olefin), poly[(polarolefin)-(non-polar olefin)], and combinations thereof.

The following expressions describe the molecular weight of a collectionof polymer chains “weight average molecular weight”, “M_(w)” and the“number average molecular weight”, “M_(n)”. These are defined asfollows:M _(w)=Σ(W _(i) M _(i))/ΣW _(i)=Σ(N _(i) M _(i) ²)/ΣN _(i) M _(i)M _(n) =ΣW _(i)/Σ(W _(i) /M _(i))=Σ(N _(i) M _(i))/ΣN _(i)

-   -   where:        -   M_(i)=molar mass of i^(th) component of distribution        -   W_(i)=weight of i^(th) component of distribution        -   N_(i)=number of chains of i^(th) component            and the summations are over all the components in the            distribution. M_(w) and M_(n) are typically computed from            the MWD as measured by Gel Permeation Chromatography (see            the Experimental Section). The value for “M_(w)/M_(n)” is            referred to as the “MWD polydispersity”.

The “average particle size” determined for a collection of polymerparticles, varies somewhat according to method of determination (e.g.,by DCP or BI-90, as described herein below), but is approximately, oridentically, “the weight average particle size”, “d_(w)”, also describedherein below.

Herein, the term “particle size distribution” and the acronym “PSD” areused interchangeably. Used herein, “PSD polydispersity” is a descriptionof the distribution of particle sizes for the plural polymer particlesof the invention. PSD polydispersity is calculated from the weightaverage particle size, d_(w), and the number average particle size,d_(n), according to the expressions:PSD Polydispersity=(d _(w))/(d _(n)),

-   -   where d_(n)=Σn_(i)d_(i)/Σn_(i)        -   d_(w)=Σn_(i)d_(i)d_(i)/Σn_(i)d_(i), and    -   where n_(i) is the number of particles having the particle size        d_(i)

A “monodisperse” distribution (herein, MWD or PSD) refers to adistribution having a polydispersity of exactly 1.

A “supercritical fluid” (“SCF”) is a substance above its criticaltemperature and critical pressure (i.e., its “critical point”). Forcarbon dioxide, the critical temperature is 31° C. and the criticalpressure is 1070 psi. Above the critical point of a fluid, furthercompression does not cause formation of a liquid (see Chem. Rev., 1999,99, pp. 565–602.

Each metal atom pair of the cationic metal-pair complex of the presentinvention includes a single “first metal atom” represented by the symbol“M¹” (“metal atom M¹”) and a single “second metal atom” represented bythe symbol “M²” (“metal atom M²”). The first metal atom of the cationicmetal-pair complex has five (5) occupied coordination sites, and is ametal atom selected from: iron, cobalt, ruthenium, rhodium, chromium,and manganese; or iron, cobalt, and chromium. The second metal atom ofthe cationic metal-pair complex can have: four (4) occupied coordinationsites; five (5) occupied coordination sites; or six (6) occupiedcoordination sites. When the second metal atom of the cationicmetal-pair complex has four (4) occupied coordination sites, that secondmetal atom is a metal atom selected from: nickel, palladium, copper,iron, cobalt, rhodium, chromium, and manganese; nickel, palladium,copper, iron, and cobalt; or nickel and palladium. When the second metalatom of the cationic metal-pair complex has five (5) occupiedcoordination sites, that second metal atom is a metal atom selectedfrom: iron, cobalt, ruthenium, rhodium, chromium, and manganese; oriron, cobalt, and chromium. When the second metal atom of the cationicmetal-pair complex has six (6) occupied coordination sites, that secondmetal atom is a metal atom selected from: copper, iron, cobalt,ruthenium, rhodium, chromium, and manganese; or copper, iron, cobalt,and chromium.

Because the cationic metal-pair complex of the present invention is madefrom the precursor complex of the present invention, it follows thatwhen a cationic complex is made from one or more precursor complexes,metal atoms M¹ and M² of a cationic metal-pair complex will be,respectively, the same as any metal atoms M¹ and M² of the precursorcomplex(s), from which that cationic metal-pair complex was made. It isfurther the case that when the precursor complex is a “full-(metal-pair)precursor complex”, both M¹ and M² will be present in the precursorcomplex. When the precursor complex is either a “first semi-(metal-pair)precursor complex” or a “second semi-(metal-pair) precursor complex”, asingle metal atom, either M¹ or M² will be present. Therefore, the firstmetal atom of the precursor complex, has five (5) occupied coordinationsites, and is a metal atom selected from: iron, cobalt, rhodium, andmanganese; or iron, cobalt, and chromium. The second metal atom of theprecursor complex can have: four (4) occupied coordination sites; five(5) occupied coordination sites; or six (6) occupied coordination sites.When the second metal atom of the precursor complex has four (4)occupied coordination sites, that second metal atom is a metal atomselected from: nickel, palladium, copper, iron, cobalt, rhodium,chromium, and manganese; nickel, palladium, copper, iron, and cobalt; ornickel and palladium. When the second metal atom of the precursorcomplex has five (5) occupied coordination sites, that second metal atomis a metal atom selected from: iron, cobalt, rhodium, and manganese; oriron, cobalt, and chromium. When the second metal atom of the precursorcomplex has six (6) occupied coordination sites, that second metal atomis a metal atom selected from: copper, iron, cobalt, ruthenium, rhodium,chromium, and manganese; or copper, iron, cobalt, and chromium.

A precursor complex may be a full-(metal pair) precursor complex, afirst semi-(metal pair) precursor complex, or a second semi-(metal pair)precursor complex. Both first metal atom, M¹, and second metal atom, M²,are present in the full-(metal pair) precursor complex. In contrast, ifeither M¹ or M² is present in a first semi-(metal pair) precursor then,respectively, either M² or M¹ will be present in the second-(metal pair)precursor.

The combined molar percentage of first metal atom, M¹, and second metalatom, M², present in the cationic metal-pair complex of the presentinvention, based on the total of all M¹-type metal atoms and M²-typemetal atoms present in any catalyst complexes of the catalyticcomposition of the present invention, is: at least 25, at least 50, atleast 75, at least 90, or at least 95; and no more than 100; no morethan 99; or no more than 97, based on the total moles of M¹ and M²

The “through-space internuclear distance” for a metal atom pair of thepresent invention is: at least 1.5 Angstroms (Å=0.0001 micron), at least2 Å, at least 3 Å, or at least 4 Å; and no more than 20 Å, no more than15 Å, no more than 10 Å, or no more than 6 Å.

Any monodentate or multidentate ligand may be a first ligand of set L¹or a second ligand of set L² of the present invention, provided thatconstraints (e.g., electronic, steric, and other spatial constraints)which exist for the ligand in any given cationic metal-pair complex, orprecursor complex allow that monodentate or multidentate ligand toparticipate in at least one coordination bond with the correspondingmetal atom (M¹ for ligand set L¹; and M² for ligand set L²) of ametal-atom pair.

When both set L¹ and set L² are present in the same cationic metal-paircomplex or in the same precursor complex, the first and second ligandsthat are, respectively, members of those sets may be identical ordifferent ligands within a given set (i.e., L¹, L²), and the ligands ofset L¹ may be the same or different from those of set L². First ligandsand second ligands may be, independently, selected from the followingnon-exhaustive lists of ligand types wherein at least one atom selectedfrom Group 14, 15, 16, and 17 participates in at least one coordinationbond of the present invention.

Any multidentate ligand may also be a third ligand of set L³ of thepresent invention, provided that constraints (e.g., electronic, steric,and other spatial constraints) which obtain for the ligand in anyspecific cationic metal-pair complex, or full-(metal pair) precursorcomplex allow that multidentate ligand to simultaneously participate inat least one coordination bond with each of the metals of a metal-atompair of that complex.

Similarly, lists of labile ligand, hemilabile ligand, anionichydrocarbyl containing radical, activator, weakly coordinating anion,diluents, and monomer types, as well as specific example, providedherein are meant to be illustrative and not exhaustive. Further, theability of a given labile ligand, hemilabile ligand, or anionichydrocarbyl containing radical to form a coordination bond with one, orboth, metal atoms of a metal atoms pair of a particular cationicmetal-pair complex or precursor complex of the present invention, willdepend upon the constraints (e.g., electronic, steric, and other spatialconstraints) which exist for that labile ligand, hemilabile ligand, oranionic hydrocarbyl containing radical.

When mono- and multi-dentate ligands are indicated structurally or bychemical name herein, usage may be made of the designation of one ormore substituents on a ligand as an “R-group” indicated by a capital“R”, with or without a superscript. Although such notation, common inthe art of organometallic chemistry and chemistry in general, isretained herein for describing substituents of ligands, it isunderstood, herein, that these “R-group” notations do not refer to thefirst or second anionic hydrocarbyl containing radicals of set R¹ andset R², respectively, of the cationic complex, or of the precursorcomplex, of the present invention. Similarly, it is understood that anyR-group notations used herein to describe, for example, substituents oflabile ligands, or substituents of hemilabile ligands, or substituentsof activators, or substituents of weakly coordinating anions, orsubstituents of ethylenically unsaturated monomers, do not refer to thefirst or second anionic hydrocarbyl containing radicals of set R¹ andset R², respectively, of the present invention.

Representative neutral electron donor ligands include amines; pyridines,organophosphorus containing compounds, and arsines and stibines, of theformula: E(R³)₃, wherein E is arsenic or antimony, and R³ isindependently selected from hydrogen, linear and branched C₁–C₁₀ alkyl,C₅–C₁₀ cycloalkyl, linear and branched C₁–C₁₀ alkoxy, allyl, linear andbranched C₂–C₁₀ alkenyl, C₆–C₁₂ aryl, C₆–C₁₂ aryloxy, C₆–C₁₂ arylsufides(e.g., PhS), C₇–C₁₈ aralkyl, cyclic ethers and thioethers, tri(linearand branched C₁–C₁₀ alkyl)silyl, tri(C₆–C₂ aryl)silyl, tri(linear andbranched C₁–C₁₀ alkoxy)silyl, triaryloxysilyl, tri(linear and branchedC₁–C₁₀ alkyl)siloxy, and tri(C₆–C₁₂ aryl)siloxy, each of the foregoingsubstituents can be optionally substituted with linear or branched C₁–C₅alkyl, linear or branched C₁–C₅ haloalkyl, C₁–C₅ alkoxy, halogen, andcombinations thereof.

Representative pyridines include pyridine, lutidine (including 2,3-;2,4-; 2,5-; 2,6-; 3,4-; and 3,5-substituted), picoline (including 2-,3-,or 4- substituted), 2,6-di-t-butylpyridine, and 2,4-di-t-butylpyridine.

Representative arsines include triphenylarsine, triethylarsine, andtriethoxysilylarsine.

Representative stibines include triphenylstibine andtrithiophenylstibine.

Suitable amine ligands can be selected from amines of the formulaN(R⁴)₃, wherein R⁴ independently represents hydrogen, linear andbranched C₁–C₂₀ alkyl, linear and branched C₁–C₂₀ haloalkyl, substitutedand unsubstituted C₃–C₂₀ cycloalkyl, substituted and unsubstitutedC₆–C₁₈ aryl, and substituted and unsubstituted C₇–C₁₈ aralkyl. Whensubstituted, the cycloalkyl, aryl and aralkyl groups can bemonosubstituted or multisubstituted, wherein the substituents areindependently selected from hydrogen, linear and branched C₁–C₁₂ alkyl,linear and branched C₁–C₅ haloalkyl, linear and branched C₁–C₅ alkoxy,C₆–C₁₂ aryl, and halogen selected from chlorine, bromine, and fluorine.Representative amines include but are not limited to ethylamine,triethylamine, diisopropylamine, tributylamine, N,N-dimethylaniline,N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-4-t-octylaniline, andN,N-dimethyl-4-hexadecylaniline.

The organophosphorus containing ligands include phosphines, phosphites,phosphonites, phosphinites and phosphorus containing compounds of theformula: P(R3) g [X′(R3)h] 3-g,-wherein X′ is oxygen, nitrogen, orsilicon, R3 is as defined above and each R3 substituent is independentof the other, g is 0, 1, 2, or 3, and h is 1, 2, or 3, with the provisothat when X′ is a silicon atom, h is 3, when X′ is an oxygen atom h is1, and when X′ is a nitrogen atom, h is 2. When g is 0 and X′ is oxygen,any two or 3 of R3 can be taken together with the, oxygen atoms to whichthey are attached to form a cyclic moiety. When g is 3 any two of R3 canbe taken together with the phosphorus atom to which they are attached torepresent a phosphacycle.

Illustrative phosphine ligands include, but are not limited totrimethylphosphine, triphenylphosphine,tri(trifluoromethylphenyl)phosphine, allyldiphenylphosphine,tris(trimethylsilyl)phosphine, and tris(pentafluorophenyl)phosphine.

The phosphine ligands can also be selected from phosphine compounds thatare water-soluble thereby imparting the resulting cationic metal-paircomplexes with solubility in aqueous media. Illustrative phosphines ofthis type include but are not limited to ionic or ionizable substitutedphosphines such as 4-(diphenylphosphine)benzoic acid, sodium2-(dicyclohexylphosphino)ethanesulfonate, and2-(dicyclohexylphosphino)-N,N,N-trimethylethanaminium iodide.

Illustrative phosphite ligands include triethylphosphite,dicyclohexylphosphite, and tri(hexafluoroisopropyl)phosphite.

Illustrative phosphinite ligands include methyl diphenylphosphinite andethyl diphenylphosphinite.

Illustrative phosphonite ligands include diphenyl phenylphosphonite anddiethyl phenylphosphonite.

The multidentate ligands of the present invention include multidentateligands containing identical or different donor atoms selected fromGroup 14, 15, 16, and 17 atoms. The substituents covalently bonded tothose donor atoms selected from Group 14, 15, 16, and 17 atoms may beany of those bound to the Group 14, 15, 16, and 17 atoms of themonodentate ligands of the present invention.

Illustrative bidentate phosphine ligands of the present inventioninclude (R)-(+)-2,2′-Bis(diphenylphosphino)-1,1′-binaphthy, and1,2-bis(diphenylphosphino)ethane.

Additional neutral electron ligands useful in the present invention aredisclosed in U.S. Pat. No. 6,455,650.

N-heterocyclic carbene ligands, suitable for use with the presentinvention include saturated and unsaturated substituted andunsubstituted imidazolidine having a structure according to one ofstructures (A)–(D):

wherein R⁹, R¹⁰, R^(10′), R¹¹, R^(11′), R¹², R^(12′), R¹³, R^(13′) andR¹⁴ are each independently a hydrogen or a substituted or unsubstitutedsubstituent selected from C1–C20 alkyl, C2–C20 alkenyl, C2–C20 alkynyl,aryl, C1–C20 carboxylate, C1–C20 alkoxy, C 2–C20 alkenyloxy, C2–C20alkynyloxy, aryloxy, C2–C20 alkoxycarbonyl, C1–C20 alkylthio, C1–C20alkylsulfonyl, C1–C20 alkylsulfinyl, and silyl; and connecting group Zmay be selected from C1–C20 alkyl, aryl, C1–C20 carboxylate, C1–C20alkoxy, C2–C20 alkenyloxy, C2–C20 alkynyloxy, aryloxy, C2–C20alkoxycarbonyl, C1–C20 alkylthio, C1–C20 alkylsulfonyl, C1–C20alkylsulfinyl, and silyl.

In one aspect, at least one of the R⁹, R¹⁰, R^(10′), R¹¹, R^(11′), R¹²,R^(12′), R¹³, R^(13′) and R¹⁴ substituent groups is substituted with atleast one moiety selected from C1–C10 alkyl, C1–C10 alkoxy, and arylwhich in turn may each be further substituted with at least one groupselected from a halogen, a C1–C5 alkyl, C1–C5 alkoxy and phenyl.

In another aspect, at least one of the R⁹, R¹⁰, R^(10′), R¹¹, R^(11′),R¹², R^(12′), R¹³, R^(13′) and R¹⁴ substituent groups further includesat least one functional group. Functional groups suitable for use inthese substituent groups include, for example, hydroxyl, thiol, alcohol,sulfonic acid, phosphine, thioether, ketone, aldehyde, ester, ether,amine, imine, amide, imide, imido, nitro, carboxylic acid, disulfide,carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, acetal,ketal, boronate, cyano, cyanohydrin, hydrazine, oxime, hydrazide,enamine, sulfone, sulfide, sulfenyl and halogen.

In another aspect, R¹⁰, R^(10′), R¹¹, R^(11′), R¹², R^(12′), R¹³, andR^(13′) are each independently selected from hydrogen, methyl, aralkyland aryl and R⁹ and R¹⁴ are each independently selected from substitutedor unsubstituted C1–C10 alkyl, C1–C10 cycloalkyl, C2–C10 alkenyl,aralkyl and aryl.

In another aspect, R¹⁰, R^(10′), R¹¹, R^(11′), R¹², R^(12′), R¹³, andR^(13′) are each hydrogen and R⁹ and R¹⁴ substituents are eachindependently substituted or unsubstituted and are selected from phenyl,vinyl, methyl, isopropyl, tert-butyl, neopentyl and benzyl.

In another aspect, R¹⁰, R^(10′), R¹¹, R^(11′), R¹², R^(12′), R¹³, andR^(13′) are each hydrogen and R⁹ and R¹⁴ substituents are eachindependently substituted or unsubstituted and are selected from phenyl,vinyl, methyl, isopropyl, tert-butyl, neopentyl and benzyl; and whereinat least one of the substituents R⁹ and R¹⁴ is substituted with at leastone moiety selected from C1–C5 alkyl, C1–C5 alkoxy, phenyl and afunctional group. Functional groups suitable for use with this aspect ofthe present invention include, for example, hydroxyl, thiol, thioether,ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylicacid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy,carbamate and halogen.

In another aspect, R⁹ and R¹⁴ are each independently substituted orunsubstituted aryl.

In another aspect, R⁹, R¹⁰, R^(10′), R¹¹, R^(11′), R¹², R^(12′), R¹³,R^(13′) and R¹³ are linked to form a substituted or unsubstituted,saturated or unsaturated ring structure.

In another aspect, R⁹, R¹⁰, R^(10′), R¹¹, R^(11′), R¹², R^(12′), R¹³,R^(13′) and R¹⁴ are linked to form a substituted or unsubstituted,saturated or unsaturated ring structure, wherein the ring structurecontains substituents selected from hydrogen, methyl and substituted orunsubstituted aryl, aralkyl, C2–C10 alkenyl, C1–C10 cycloalkyl andC1–C10 alkyl.

In another aspect, R⁹, R¹⁰, R^(10′), R¹¹, R^(11′), R¹², R^(12′), R¹³,R^(13′) and R¹⁴ are linked to form a substituted or unsubstituted,saturated or unsaturated ring structure, wherein the ring structurecontains substituents selected from alkoxy, aryloxy and functionalgroups selected from hydroxyl, thiol, thioether, ketone, aldehyde,ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide,carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen.

In another aspect, R¹⁰, R^(10′), R¹³ and R^(13′) are each independentlya hydrogen, a phenyl or together form a cycloalkyl or an aryl optionallysubstituted with at least one moiety selected from C1–C10 alkyl, C1–C10alkoxy, aryl and a functional group selected from hydroxyl, thiol,thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro,carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,carboalkoxy, carbamate, and halogen; and R⁹ and R¹⁴ are eachindependently C1–C₁₀ alkyl or aryl optionally substituted with C1–C5alkyl, C1–C5 alkoxy, aryl or a functional group selected from hydroxyl,thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide,nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,carboalkoxy, carbamate and halogen.

In another aspect, R¹⁰, R^(10′), R¹⁴ and R^(14′) are both hydrogen orphenyl, or together form a cycloalkyl group; if present, R¹¹, R^(11′),R¹² and R^(12′) are each hydrogen; and R⁹ and R¹⁴ are each selected fromsubstituted or unsubstituted aryl.

In another aspect, R⁹ and R¹⁴ are independently of structure (E):

wherein R¹⁵, R¹⁶, and R¹⁷ are each independently hydrogen, C1–C10 alkyl,C1–C10 alkoxy, aryl or a functional group selected from hydroxyl, thiol,thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro,carboxylic acid, disulfide, carbonate, isocyanate, carbodimide,carboalkoxy, carbamate and halogen.

In another aspect, R⁹ and R¹⁴ are independently of structure (E),wherein R¹⁵, R¹⁶, and R¹⁷ are each independently selected from hydrogen,methyl, ethyl, propyl, isopropyl, hydroxyl and halogen.

In another aspect, R⁹ and R¹⁴ are independently of structure (E),wherein R¹⁵, R¹⁶, and R¹⁷ are each methyl.

In another aspect, the connecting group, Z, may be substituted with oneor more moieties selected from C1–C10 alkyl, C1–C10 alkoxy and aryl;which in turn may each be further substituted with one or more groupsselected from a halogen, a C1–C5 alkyl, C1–C5 alkoxy and phenyl.

In another aspect, the connecting group, Z, may further include one ormore functional groups. Functional groups suitable for use in connectinggroup, Z, include, for example, hydroxyl, thiol, alcohol, sulfonic acid,phosphine, thioether, ketone, aldehyde, ester, ether, amine, imine,amide, imide, imido, nitro, carboxylic acid, disulfide, carbonate,isocyanate, carbodiimide, carboalkoxy, carbamate, acetal, ketal,boronate, cyano, cyanohydrin, hydrazine, oxime, hydrazide, enamine,sulfone, sulfide, sulfenyl and halogen.

Additional moieties suitable as bridging moieties include methylenes,alkylenes, halides, and pseudohalides. The methylenes (i.e., CR₂) andalkylenes (i.e., (CR₂)_(n), n=1–24), may have R-groups which,independently, may be C1–C20 alkyl or branched alkyl, mono andmulti-ring aryl. Further, any of the carbons of these methylenes andalkylenes may be further substituted with functional groups. Halides andpseudohalides may be and first ligand, second ligands, or bridgingmoieties. Suitable halides include, for example, fluoride, chloride,bromide, and iodide. Suitable pseudohalides include, for example,cyanide, isocyanide, alkoxides, thioalkoxides, amines, and phosphides.Hydride may further be a bridging moiety.

Hemilabile ligands contain at least two different types of donor sites,wherein at least one donor site is capable of acting as a “non-labiledonor site”, and at least one donor site is capable of acting as a“labile donor site”. Typically, a labile donor site is easily displacedfrom a coordination bond with a metal by, for example, the donor sitesof labile ligands (e.g., solvent molecules) and by ethylenicallyunsaturated monomer. It, therefore, follows that a labile donor site ofa hemilabile ligand is easily displaced by strongly coordinatingligands. In contrast, a non-labile donor site is difficult to displacefrom coordination bond with a metal. Therefore, when a hemilabile ligandis attached to a metal pair of a cationic metal-pair complex orprecursor complex of the present invention, the formalism for assigningsubscripts to any cationic metal-pair complex formula or precursorcomplex formula is as follows: when a hemilabile ligand is bound to asingle metal atom of a metal atom pair, any coordination bonds formed byany of the donor sites (labile or non-labile) of that hemilabile ligandwill be treated as coordination bonds of first or second ligands; when ahemilabile ligand is bound to both metal atoms of a metal atom pair, anycoordination bonds formed by any of the donor sites (labile ornon-labile) of that hemilabile ligand will be treated as coordinationbonds of a bridging moiety. Further description of hemilabile ligandsmay be found in: Braunstein, P.; Naud, F. Angew. Chem. Int. Ed. 2001,40, 680; Slone, C. S.; Weinberger, D. A.; Mirkin, C. A. Prog. Inorg.Chem. 1999, 48, 233, and the hemilabile ligands of the present inventioninclude those described therein.

One skilled in the art of organometallic chemistry will recognize thatthe hemilabile ligands of the present invention may be any hemilabileligand. For illustrative purposes, a non-exhaustive list of hemilabilephosphine ligands is described. Similar lists exist for other Group 14,15, 16, and 17 atom containing ligands. By hemilabile phosphine ligandis meant a phosphine ligand containing an additional heteroatomsubstituent, (e.g., oxygen or sulfur), capable of weakly complexing ametal atom. Included in the hemilabile phosphine ligands of the presentinvention are hemilabile phosphine ligands represented by the formulaP(R²⁴)₂Q wherein R²⁴ independently represents linear and branched(C₁–C₁₂) alkyl, cycloalkyl and (C₆–C₁₄) aryl and substituted aryl, and Qrepresents an organic moiety containing a heteroatom, selected fromphosphorous, oxygen, and sulfur and combinations thereof. Examples ofthe Q substituent include but are not limited to -dibenzothiophene,ortho- alkoxyphenyl-, ortho-alkoxycarbonylphenyl-, wherein the alkoxygroup is linear or branched (C₁–C₅) alkoxy; —(CH₂)_(q)S(═O)C₆H₅,—(CH₂)_(q)SC₆H₅, —(CH₂)_(q)P(═O)(C₆H₅)₂, —(CH₂)_(q)P(═S)(C₆H₅)₂, whereinq is 2 or 3. Example of ligands excluded from this class of hemiligandsare the strongly chelating ligands, e.g., the diphosphines such asdiphenylphosphinoethane and diphenylphosphinopropane. Specific examplesof suitable hemilabile phosphine ligands are illustrated below:

The following hemilabile ligands are shown coordinated to a metal atom,M, through a non-labile donor site. Labile donor sites, available forweak bonding to the same metal atom, or another metal atom are indicatedby asterisk.

A non-exhaustive list of ligands further illustrating bridging moietiesof the present invention, is found in Table I. These and other suitablebridging moieties are disclosed in Gavrilova, A. L.; Bosnich, B. Chem.Rev. 2004, 104, 349.

TABLE I Examples of bridging moieties of the present invention. Bridgingunit name Bridging unit Metal binding mode Halide, Pseudohalide

Methylene, (methylene)_(n)

Carboxylate

Formamidinate

Pyrazolate

Triazolate

Oxadiazole

Triadiazole

Pyridazine andPhthalazine

1,8-Naphthyridine

Phenolate, Alkoxide

Thiophenolate

Disulfide

Phosphide

An additional illustrative example of a bridging moiety is “NON”:

depicted here in a cationic metal-pair complex in which both M¹ and M²are palladium.

Any monodentate or multidentate labile ligand may be a first labileligand of set S¹ or a second ligand of set S² of the present invention,provided that constraints (e.g., electronic, steric, and other spatialconstraints) which exist for that labile ligand in any given cationicmetal-pair complex, or precursor complex allow that monodentate ormultidentate ligand to participate in at least on coordination bond withthe corresponding metal atom (M¹ for labile ligand set S¹; and M² forlabile ligand set S²) of a metal-atom pair. Further, any multidentatelabile ligand may simultaneously participate in at least onecoordination bond of each metal atom in a metal atom pair. In such case,the labile ligand is acting as a bridging moiety, so the formalism forassigning subscripts to any cationic metal-pair complex formula orprecursor complex formula is as follows: when a labile ligand is boundto both metal atoms of a metal atom pair, any coordination bonds formedby labile donor sites of that labile ligand will be treated ascoordination bonds of a bridging moiety (ie., of set L³).

A non-exhaustive list of the labile neutral electron donor ligands ofthe present invention includes solvents such as methylene chloride,CHCl₃, ClCH₂CH₂Cl, acrylonitrile, tetrahydrofuran, toluene, benzene,chlorobenzene, and polar monomers, as well as any other diluentstypified by those found in the list of diluents, herein, which are ableto donate electron density to a metal atom coordination site to form acoordination bond. Further, molecules such as, for example, dioxane,crown ethers, other polyethers, and cyclodextrins typify labile ligandscapable of bridging between the metal atoms of a metal atom pair, and,where electronic, steric, and special constraints permit, between, oramong metal atom pairs. One skilled in the art of organometallicchemisty will understand that a labile ligand may participate in acoordination bond with a one or both metal atoms of a metal atom pair.Alternatively, a labile ligand may be more loosely associated as part ofa solvation sphere which may, in some cases, surround any of thecationic metal-pair complexes or precursor complexes of the presentinvention. According to common practice in the art, these more looselyassociated molecules of the solvation sphere are not explicitlyindicated in the cationic metal-pair complex formula or the precursorcomplex formula.

R¹ and R² represent anionic hydrocarbyl containing radicals, and appearin the formulae for the precursor complexes and for the cationicmetal-pair complex of the present invention. When both R¹ and R² arepresent in the same precursor complex or in the same cationic metal-paircomplex, they may be identical or different entities. R¹ and R² may be,independently, selected from the following non-exhaustive lists of typesof anionic hydrocarbyl containing radical and of specific examples ofanionic hydrocarbyl containing radical.

First and second anionic hydrocarbyl containing radicals include, butare not limited to, hydrogen, linear and branched C1–C20 alkyl, C5–C10cycloalkyl, linear and branched C2–C20 alkenyl, C6–C15 cycloalkenyl,allylic and methallylic ligands, crotyl ligands, or canonical formsthereof, C6–C30 aryl, C6–C30 heteroatom containing aryl, and C7–C30aralkyl, each of the foregoing groups can be optionally substituted withhydrocarbyl containing and/or heteroatom substituents preferablyselected from linear or branched C1–C5 alkyl, linear or branched C1–C5haloalkyl, linear or branched C2–C5 alkenyl and haloalkenyl, halogen,sulfur, oxygen, nitrogen, phosphorus, and phenyl optionally substitutedwith linear or branched C1–C5 alkyl, linear or branched C1–C5 haloalkyl,and halogen. R¹ and R² also represent anionic containing ligands of theformula R″C(O)O, R″C(O) CHC(O)R″, R″C(O)S, R″C(S)O, R″C(S)S, R″O, andR″₂N.

Additional representative examples of anionic ligands:

wherein the various R-groups may be: C1–C12 linear, branched, or cyclicand polycyclic alkyl; aryl or polycyclic aryl; or functional groups; andthe alkyl and aryl groups may be further substituted with functionalgroups.

A “leaving group” (“Y”) is capable of being removed from a precursorcomplex of the present invention by the action of an activatorcomponent. A leaving group (e.g., a halide or pseudohalide) may be boundto both metals or a single metal of a metal pair of a full-(metal pair)precursor complex, or bound to the single metal atom of a semi-(metalpair) precursor complex.

Additional examples of anionic hydrocarbyl containing ligands aredisclosed in U.S. Pat. No. 6,455,650; R. G. Guy and B. L. Shaw, Advancesin Inorganic Chemistry and Radiochemistry, Vol. 4, Academic Press Inc.,New York, 1962; J. Birmingham, E. de Boer, M. L. H. Green, R. B. King,R. Köster, P. L. I. Nagy, G. N. Schrauzer, Advances in OrganometallicChemistry, Vol. 2, Academic Press Inc., New York, 1964; W. T. Dent, R.Long and A. J. Wilkinson, J. Chem. Soc., 1964 1585; and H. C. Volger,Rec. Trav. Chim. Pay Bas, 1969 88 225.

A “WCA” is a “weakly coordinating anion”. The weakly coordinating anionis an anion that is only weakly coordinated to the cationic metal-paircomplex. The WCA is sufficiently labile to be displaced by a neutralLewis base, solvent or monomer. More specifically, the WCA functions asa stabilizing anion to the cationic metal-pair complex and does nottransfer to the cationic metal-pair complex to form a neutral product.The WCA is relatively inert in that it is non-oxidative, non-reducing,and non-nucleophilic.

The weakly coordinating anion can be selected, for example, from boratesand aluminates, boratobenzene anions, carborane halocarborane anions,antimony halide anions (e.g., SbF₆), phosphorus halide anions (e.g.,PF₆), and boron halide anions (e.g., BF₄). The borate and aluminateweakly coordinating anions are represented by the structures II and IIIbelow:[Q(R⁴)(R⁵) (R⁶)(R⁷)]  structure II[Q(OR⁸)(OR⁹)(OR¹⁰)(OR¹¹)]  IIIwherein, in structure II, Q is boron or aluminum and R⁴, R⁵, R⁶, and R⁷independently represent fluorine, linear and branched C₁–C10 alkyl,linear and branched C₁–C10 alkoxy, linear and branched C3–C5haloalkenyl, linear and branched C3–C12 trialkylsiloxy, C18–C36triarylsiloxy, substituted and unsubstituted C6–C30 aryl, andsubstituted and unsubstituted C6–C30 aryloxy groups wherein R⁴ to R⁷ cannot all simultaneously represent alkoxy or aryloxy groups. Whensubstituted the aryl groups can be monosubstituted or multisubstituted,wherein the substituents are independently selected from linear andbranched C₁–C5 alkyl, linear and branched C₁–C5 haloalkyl, linear andbranched C₁–C5 alkoxy, linear and branched C₁–C5 haloalkoxy, linear andbranched C₁–C12 trialkylsilyl, C6–C18 triarylsilyl, and halogen selectedfrom chlorine, bromine, and fluorine, preferably fluorine.Representative borate anions under Structure II include but are notlimited to tetrakis(pentafluorophenyl)borate,tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate,tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate,phenyltris(perfluorophenyl)borate,tetrakis(1,2,2-trifluoroethylenyl)borate,tetrakis(4-tri-i-propylsilyltetrafluorophenyl)borate,tetrakis(4-dimethyl-tert- butylsilyltetrafluorophenyl)borate,(triphenylsiloxy) tris(pentafluorophenyl)borate,(octyloxy)tris(pentafluorophenyl)borate,tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,andtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate.

Representative aluminate anions under Structure II include but are notlimited to tetrakis(pentafluorophenyl)aluminate, tris(perfluorobiphenyl)fluoroaluminate, (octyloxy)tris(pentafluorophenyl)aluminate,tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, andmethyltris(pentafluorophenyl) aluminate.

In Structure III Q is boron or aluminum, R⁸, R⁹, R¹⁰, and R¹¹independently represent linear and branched C₁–C₁₀ alkyl, linear andbranched C₁–C10 haloalkyl, C2–C₁₀ haloalkenyl, substituted andunsubstituted C6–C30 aryl, and substituted and unsubstituted C7–C30aralkyl groups, subject to the proviso that at least three of R⁸ to R¹¹must contain a halogen containing substituent. When substituted the aryland aralkyl groups can be monosubstituted or multisubstituted, whereinthe substituents are independently selected from linear and branchedC₁–C5 alkyl, linear and branched C₁–C5 haloalkyl, linear and branchedC₁–C5 alkoxy, linear and branched C₁–C10 haloalkoxy, and halogenselected from chlorine, bromine, and fluorine, preferably fluorine. Thegroups OR⁸ and OR⁹ can be taken together to form a chelating substituentrepresented by —O—RR¹²—O—, wherein the oxygen atoms are bonded to Q andR¹² is a divalent radical selected from substituted and unsubstitutedC6–C30 aryl and substituted and unsubstituted C7–C30 aralkyl.Preferably, the oxygen atoms are bonded, either directly or through analkyl group, to the aromatic ring in the ortho or meta position. Whensubstituted the aryl and aralkyl groups can be monosubstituted ormultisubstituted, wherein the substituents are independently selectedfrom linear and branched C₁–C5 alkyl, linear and branched C₁–C5haloalkyl, linear and branched C₁–C5 alkoxy, linear and branched C₁–C10haloalkoxy, and halogen selected from chlorine, bromine, and fluorine,preferably fluorine.

Representative borate and aluminate anions under Structure III includebut are not limited to [B(OC(CF₃)₃)₄]⁻, [B(OC(CF₃)₂(CH₃))₄]⁻,[B(OC(CF₃)₂H)₄]⁻, [Al(OC(CF₃)₂Ph)₄]⁻, [B(OCH₂(CF₃)₂)₄]⁻,[Al(OC(CF₃)₂C₆H₄CH₃)₄]⁻, [Al(OC(CF₃)₃)₄]⁻, [Al(OC(CF₃)(CH₃)H)₄]⁻,[Al(OC(CF₃)₂H)₄]⁻, [Al(OC(CF₃)₂C₆H₄-4-i-Pr)₄]⁻,[Al(OC(CF₃)₂C₆H₄-t-butyl)₄]-, [Al(OC(CF₃)₂C₆H₄-4-SiMe₃)₄]⁻,[Al(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄]⁻,[Al(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄]⁻,[Al(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄]⁻, [Al(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄]⁻, and[Al(OC(CF₃)₂C₆F₅)₄]⁻.

Representative boratobenzene anions include but are not limited to[1,4-dihydro-4-methyl-1-(pentafluorophenyl)]-2-borate,4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-borate,1-fluoro-1,2-dihydro-4-(pentafluorophenyl)-2-borate, and1-[3,5-bis(trifluoromethyl)phenyl]-1,2-dihydro-4-(pentafluorophenyl)-2-borate.

The carborane and halocarborane anions useful as the weakly coordinatinganion include but are not limited to CB₁₁(CH₃)₁₂ ⁻, CB₁₁H₁₂ ⁻,1-C₂H₅CB₁₁H₁₁, 1-Ph₃SiCB₁₁H₁₁ ⁻, 1-CF₃CB₁₁H₁₁ ⁻, 12-BrCB₁₁H₁₁ ⁻,12-BrCB₁₁H₁₁ ⁻, 7,12-Br₂CB₁₁H₁₀ ⁻, 12-ClCB₁₁H₁₁ ⁻, 7,12-Cl₂CB₁₁H₁₀ ⁻,1-H-CB₁₁F₁₁ ⁻, 1-CH₃—CB₁₁F₁₁ ⁻, 1-CF₃—CB₁₁F₁₁ ⁻, 12-CB₁₁H₁₁F⁻,7,12-CB₁₁H₁₁F₁₂ ⁻, 7,9,12-CB₁₁H₁₁F₃ ⁻, CB₁₁H₆Br₆ ⁻, 6-CB₉H₉F⁻,6,8-CB₉H₈F₂ ⁻, 6,7,8-CB₉H₇F₃ ⁻, 6,7,8,9-CB₉H₆F₄ ⁻, 2,6,7,8,9-CB₉H₅F₅ ⁻,CB₉H₅Br₅ ⁻, CB₁₁H₆Cl₆ ⁻, CB₁₁H₆F₆ ^(−, CB) ₁₁H₆F₆ ⁻, CB₁₁H₆I₆ ⁻,CB₁₁H₆Br₆ ⁻, 6,7,9,10,11,12-CB₁₁H₆F₆ ⁻, 2,6,7,8,9,10-CB₉H₅F₅ ⁻,1-H—CB₉F₉ ⁻, 12-CB₁₁H₁₁(C₆H₅)⁻, 1-C₆F₅—CB₁₁H₅Br₆ ⁻, CB₁₁Me₁₂ ⁻,CB₁₁(CF₃)₁₂ ⁻, Co(B₉C₂H₁₁)₁₂ ⁻, CB₁₁(CH₃)₁₂ ⁻, CB₁₁(C₄H₉)₁₂ ⁻,CB₁₁(C₆H₁₃)₁₂ ⁻, Co(C₂B₉H₁₁)₂ ⁻, Co(Br₃C₂B₉H₈)₂ ⁻ anddodecahydro-1-carbadodecaborate. The weakly coordinating anion of thepresent invention further includes any of those disclosed in U.S. Pat.No. 6,455,650.

Illustrative, but non-limiting examples of the “activator component” ofthe present invention are disclosed in publications of: Chen and Marks,such as Chem. Rev. 2000 100, 1391–1434; Coates, such as Chem. Rev. 2000100, 1223–1252; Resconi et al, such as Chem. Rev. 2000 100, 1253–1346;Fink et al, such as Chem. Rev. 2000 100, 1377–1390; Alt and Koeppl, suchas Chem. Rev. 2000 100, 1205–1222; and Hlatky, Chem. Rev. 2000 100,1347–1376, the contents of which are usefully employed in accordancewith the present invention. Activator components useful in the method ofpreparing the cationic metal-pair complex of the present invention, forexample, include: aluminum alkyls such as Al(C₂H₅)₃, Al(CH₂CH(CH₃)₂)₃,Al(C₃H₇)₃, Al((CH₂)₃CH₃)₃, Al((CH₂)₅CH₃)₃, Al(C₆F₅)₃, Al(C₂H₅)₂Cl,Al₂(C₂H₅)₃Cl₂, AlCl₃; aluminoxanes such as methylaluminoxane (MAO),modified methyl aluminoxane (MMAO), isobutylaluminoxane,butylaluminoxane, heptylaluminoxane and methylbutylaluminoxane; andcombinations thereof. Both stoichiometric and non-stoichiometricquantities of activator components are usefully employed in the presentinvention. Chemically and structurally useful aluminum compounds as wellas other activator components of Group 13 elements would be apparent tothose skilled in the art based on their respective chemical structuresand activities in preparing cationic metal-pair complexes.

The activator component further comprises hydroxyaluminoxanes.Hydroxyaluminoxanes, and methods of preparing them, are disclosed inU.S. Pat. No. 6,160,145. The hydroxyaluminoxane has a hydroxyl groupbonded to at least one of its aluminum atoms.

The alkyl aluminum compound used in forming the hydroxyaluminoxanereactant can be any suitable alkyl aluminum compound other thantrimethylaluminum. Thus at least one alkyl group has two or more carbonatoms. Preferably each alkyl group in the alkyl aluminum compound has atleast two carbon atoms. More preferably each alkyl group has in therange of 2 to about 24, and still more preferably in the range of 2 toabout 16 carbon atoms. Most preferred are alkyl groups that have in therange of 2 to about 9 carbon atoms each. The alkyl groups can be cyclic(e.g., cycloalkyl, alkyl-substituted cycloalkyl, orcycloalkyl-substituted alkyl groups) or acyclic, linear or branchedchain alkyl groups. Preferably the alkyl aluminum compound contains atleast one, desirably at least two, and most preferably three branchedchained alkyl groups in the molecule. Most preferably each alkyl groupof the aluminum alkyl is a primary alkyl group, i.e., the alpha-carbonatom of each alkyl group carries two hydrogen atoms.

Suitable aluminum alkyl compounds which may be used to form thehydroxyaluminoxane reactant include dialkylaluminum hydrides andaluminum trialkyls. Examples of the dialkylaluminum hydrides includediethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminumhydride, di(2,4,4-trimethylpentyl)aluminum hydride,di(2-ethylhexyl)aluminum hydride, di(2-butyloctyl)aluminum hydride,di(2,4,4,6,6-pentamethylheptyl)aluminum hydride,di(2-hexyldecyl)aluminum hydride, dicyclopropylcarbinylaluminum hydride,dicyclohexylaluminum hydride, dicyclopentylcarbinylaluminum hydride, andanalogous dialkylaluminum hydrides. Examples of trialkylaluminumcompounds which may be used to form the hydroxyaluminoxane includetriethylaluminum, tripropylaluminum, tributylaluminum,tripentylaluminum, trihexylaluminum, triheptylaluminum,trioctylaluminum, and their higher straight chain homologs;triisobutylaluminum, tris(2,4,4-trimethylpentyl)aluminum,tri-2-ethylhexylaluminum, tris(2,4,4,6,6-pentamethylheptyl)aluminum,tris(2-butyloctyl)aluminum, tris(2-hexyldecyl)aluminum, tris(2-heptylundecyl)aluminum, and their higher branched chain homologs;tri(cyclohexylcarbinyl)aluminum, tri(2-cyclohexylethyl)aluminum andanalogous cycloaliphatic aluminum trialkyls; andtri(pentafluoro)aluminum. Triisobutylaluminum has proven to be anespecially desirable alkyl aluminum compound for producing ahydroxyaluminoxane. Hydroxyisobutylaluminoxane (HOIBAO) is a preferredhydroxyaluminoxane. The hydroxyisobutylaluminoxane is essentially devoidof unreacted triisobutylaluminum.

Useful activator components further include aluminoxane saltcompositions (aluminoxinates) as disclosed in U.S. Pat. No. 5,922,631.Useful activator components still further include any of the liquidclathrate aluminoxanes disclosed in U.S. Pat. No. 5,670,682.

Activator components useful in the present invention further includeorganic borane compounds, inorganic borane compounds, and borate anions.Preferred examples of boron containing activator components employed inthe method of preparing the cationic metal-pair complex of the presentinvention are trifluoroborane, triphenylborane,tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane,tris(4-fluoromethylphenyl)borane, tris(pentafluorophenyl)borane,tris(tolyl)borane, tris(3,5-dimethylphenyl)borane,tris(3,5-difluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane,dimethylanilinium (pentafluorophenyl) borate,sodium[B{3,5-(CF₃)₂C₆F₃}₄], [H(OEt₂)₂[B{3,5-(CF₃)₂C₆F₃}₄]. Bothstoichiometric and non-stoichiometric quantities of activators areusefully employed using triaryl carbenium tetraarylborates,N,N-dialkylanilinium salts such as N,N-dimethylaniliniumtetra(pentafluorophenyl)borate, N,N-diethylaniliniumtetra(phenyl)borate, N,N-2,4,6-pentamethylanilinium tetraphenylborateand chemically related Group 13 compounds; dialkyl ammonium salts suchas di(i-propyl)ammonium tetra(pentafluorophenyl)borate,dicyclohexylammonium tetra(phenyl)boron and chemically related Group 13compounds; triaryl phosphonium salts such as triphenylphosphoniumtetraphenylborate, tri(methylphenyl)phosphonium tetra(phenyl)borate,tri(dimethylphenyl)phosphonium tetra(phenyl)borate and chemicallyrelated Group 13 compounds. Any complex anions or compounds forming suchanions that exhibit an ability to abstract and activate the metalcompounds would be within the scope of the “activator component” of thepresent invention. Chemically and structurally useful boron compoundswould be apparent to those skilled in the art based on their respectivechemical structures and activities in olefin polymerizations.

In the method of the present invention, the activator component ispresent in an amount of: at least 0.1 molar equivalent, at least 0.3molar equivalent, at least 0.7 molar equivalent, or at least 1.0 molarequivalent, based on leaving group Y; and no more than 5,000 molarequivalent, no more than 500 molar equivalent, no more than 5 molarequivalent, or no more than 2 molar equivalents, based on leaving groupY.

The non-polar olefinic monomers of the present invention include, forexample, unbranched aliphatic olefins having from 2 to 12 carbon atoms,branched aliphatic olefins having from 4 to 12 carbon atoms, unbranchedand branched aliphatic α-olefins having from 2 to 12 carbon atoms,conjugated olefins having 4 to 12 carbon atoms, aromatic olefins havingfrom 8 to 20 carbons, unbranched and branched cycloolefins having 3 to12 carbon atoms, unbranched and branched acetylenes having 2 to 12carbon atoms, and combinations thereof. A non-exhaustive list ofexamples of non-polar olefinic monomers of the present inventionincludes ethylene, propene, 1-butene, 1-hexene, butadiene,1,5-hexadiene, isoprene, styrene, alpha-methylstyrene, cyclopentene,cyclohexene, cyclohexadiene, norbornene, norbornadiene, cyclooctadiene,divinylbenzene, trivinylbenzene, acetylene, diacetylene, alkynylbenzene,dialkynylbenzene, ethylene/1-butene, ethylene/isopropene,ethylene/1-hexene, ethylene/1-octene, ethylene/propene,ethylene/cyclopentene, ethylene/cyclohexene, ethylene/butadiene,ethylene/1,5-hexadiene, ethylene/styrene, ethylene/acetylene,propene/1-butene, propene/styrene, propene/butadiene,propylene/1-hexene, propene/acetylene, ethylene/propene/1-butene,ethylene/propene/1-hexene, ethylene/propene/1-octene, and variouscombinations thereof.

Polar olefinic monomers of the present invention include ethylenicallyunsaturated monomers having from 2 to 60 carbon atoms and at least oneatom such as O, N, B, Al, S, P, Si, F, Cl, Br, and combinations thereof.These polar olefinic monomers include, for example: C₁–C₂₂ linear orbranched chain alkyl (meth)acrylates, bornyl (meth)acrylate, andisobornyl (meth)acrylate; hydroxyethyl (meth)acrylate, hydroxypropyl(meth)acrylate; (meth)acrylamide or substituted (meth)acrylamides; epoxycontaining (meth)acrylates such as glycidyl (meth)acrylate; styrene orsubstituted styrenes; butadiene; vinyl acetate or other vinyl ester;vinyl chloride; vinylidene chloride; vinylidene fluoride;N-butylaminoethyl (meth)acrylate, N,N-di(methyl)aminoethyl(meth)acrylate; monomers containing α,β-unsaturated carbonyl functionalgroups such as fumarate, maleate, cinnamate and crotonate; and(meth)acrylonitrile. Acid-functional methacrylic monomers include, forexample, (meth)acrylic acid, itaconic acid, crotonic acid, phosphoethyl(meth)acrylate, sulfoethyl (meth)acrylate,2-acrylamido-2-methyl-1-propanesulfonic acid, fumaric acid, maleicanhydride, monomethyl maleate, and maleic acid.

Polar olefinic monomers of the present invention further include:acrylic acid 5-oxo-tetrahydro-furan-3-yl ester, acrylic acid1,1,2-trimethyl-propyl ester, acrylic acid2-ethyl-1,3,3-trimethyl-bicyclo[2.2.1]hept-2-yl ester, acrylic acid2-ethyl-adamantan-2-yl ester, acrylic acid 2-methyl-adamantan-2-ylester, acrylic acid 4-hydroxy-adamantan-1-yl ester, acrylic acid3-hydroxy-adamantan-1-yl ester, acrylic acid5-hydroxy-2-methyl-adamantan-2-yl ester, 5H-Furan-2-one,3-Methylene-dihydro-furan-2-one, acrylic acid1,7,7-trimethyl-bicyclo[2.2.1]hept-2-yl ester, acrylic acid1-methyl-cyclopentyl ester, acrylic acid5-oxo-4-oxa-tricyclo[4.2.1.03,7]non-2-yl ester, acrylic acid1,2,3,3-tetramethyl-bicyclo[2.2.1]hept-2-yl ester, acrylic acidtert-butyl ester, acrylic acid 1-ethyl-cyclopentyl ester, acrylic acid3-oxo-4-oxa-tricyclo[5.2.1.02,6]dec-8-yl ester, and acrylic acid1-(2-oxo-tetrahydro-furan-3-yl)-ethyl ester.

Suitable fluorinated (meth)acrylic monomers useful in the presentinvention include, but are not limited to: fluoroalkyl (meth)acrylate;fluoroalkylsulfoamidoethyl (meth)acrylate; fluoroalkylamidoethyl(meth)acrylate; fluoroalkyl (meth)acrylamide; fluoroalkylpropyl(meth)acrylate; fluoroalkylethyl poly(alkyleneoxide) (meth)acrylate;fluoroalkylsulfoethyl (meth)acrylate; fluoroalkylethyl vinyl ether;fluoroalkylethyl poly(ethyleneoxide) vinyl ether; pentafluoro styrene;fluoroalkyl styrene; vinylidene fluoride; fluorinated α-olefins;perfluorobutadiene; 1-fluoroalkylperfluorobutadiene;ω-H-perfluoroalkanediol di(meth)acrylate; and β-substituted fluoroalkyl(meth)acrylate. The fluoroalkyl groups used as substituents have from 1to 20 carbon atoms and the fluoroalkyl groups may be mono-, di, tri, ortetra-fluorinated, or contain any number of fluoro-atoms, up to andincluding perfluorinated compositions.

Silicon containing polar olefinic monomers useful in the presentinvention include, for example, trimethoxysilylethyl (meth)acrylate andtrimethoxysilylpropyl (meth)acrylate.

The terms “cyclic olefin,”, “polycyclic”, “polycyclicolefin,” and“norbornene-type” monomer as used herein are interchangeable and meanthat the monomer contains at least one norbornene moiety as follows:

wherein W′″ is selected from the group including, but by no meanslimited to, an oxygen, a nitrogen with a hydrogen attached thereto, anitrogen with a linear C₁ to C₁₀ alkyl grouping attached thereto, anitrogen with a branched C₁ to C₁₀ alkyl grouping attached thereto, asulfur and a methylene group of having the formula —(CH₂)n′- wherein n′is an integer from 1 to 5.

Polycyclic monomers of the present invention include both polycyclicmonomers that are non-polar monomers and polycyclic monomer that arepolar monomer.

Polycyclic monomers suitable for use with the present invention includebicyclic monomers, for example, bicyclo[2.2.1]hept-2-ene also referredto as norbornene.

The term “norbornene-type monomer” as used herein and in the appendedclaims is meant to encompass norbornene, substituted norbornene, as wellas any substituted and unsubstituted higher cyclic derivatives thereof,provided that the subject monomer contains at least one norbornene-typemoiety or substituted norbornene-type moiety.

Norbornene-type monomers suitable for use with the present inventioninclude substituted norbornene-type monomers and higher cyclicderivatives thereof that contain a pendant hydrocarbon group or apendant functional substituent containing an oxygen atom.

Norbornene-type monomers suitable for use with the present invention mayinclude norbornene-type or polycycloolefin monomers are represented bythe structure below:

wherein each W′″ is independently defined as above; “a” is a single or adouble bond; R¹, R², R³, and R⁴ each independently represent a hydrogen,a hydrocarbyl or a functional substituent; m is an integer from 0 to 5,with the proviso that when “a” is a double bond, both (i) one of R¹ andR² is not present and (ii) one of R³ and R⁴ is not present.

The term “hydrocarbon groups” as used herein and in the appended claimsencompasses hydrogen, hydrocarbon groups, halohydrocarbon groups,perhalohydrocarbon groups and perhalocarbyl groups. In one embodiment,R¹, R², R³ and/or R⁴, may independently represent hydrogen, linear orbranched C₁–C₁₀ alkyl, linear or branched C₂–C₁₀ alkenyl, linear orbranched C₂–C₁₀ alkynyl, C₄–C₁₂ cycloalkyl, C₄–C₁₂ cycloalkenyl, C₆–C₁₂aryl, and C₇–C₂₄ aralkyl. In one embodiment, R¹ and R² or R³ and R⁴ maycollectively represent a C₁–C₁₀ alkylidenyl group. Representative alkylgroups include, but are by no means limited to, methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl,hexyl, heptyl, octyl, nonyl and decyl. Representative alkenyl groupsinclude, but are by no means limited to, vinyl, allyl, butenyl andcyclohexenyl. Representative alkynyl groups, include but are by no meanslimited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl and 2-butynyl.Representative cycloalkyl groups include, but are by no means limitedto, cyclopentyl, cyclohexyl and cyclooctyl substituents. Representativearyl groups include, but are by no means limited to, phenyl, naphthyland anthracenyl. Representative aralkyl groups include, but are by nomeans limited to, benzyl and phenethyl. Representative alkylidenylgroups include, but are by no means limited to, methylidenyl andethylidenyl groups.

In one embodiment, the perhalohydrocarbon groups may includeperhalogenated phenyl and alkyl groups. The halogenated alkyl groupsuseful in the invention are partially or fully halogenated and arelinear or branched, and have the formula C_(z)W″_(2z+1) wherein W″ isindependently selected from halogen and hydrogen and z is an integer of1 to 20. In another embodiment, each W″ is independently selected fromhydrogen, chlorine, fluorine and bromine. In another embodiment, each W″is independently selected from hydrogen and fluorine.

In one embodiment, the perfluorinated substituents includeperfluorophenyl, perfluoromethyl, perfluoroethyl, perfluoropropyl,perfluorobutyl and perfluorohexyl. In addition to the halogensubstituents, the cycloalkyl, aryl, and aralkyl groups of the presentinvention may be further substituted with linear or branched C₁–C₅ alkyland haloalkyl groups, aryl groups and cycloalkyl groups.

When the pendant group(s) is(are) a functional substituent, R¹, R², R³may R⁴ independently represent a radical selected from(CH₂)_(n)—CH(CF₃)₂—O—Si(Me)₃, —(CH₂)_(n)—CH(CF₃)₂—O—CH₂—O—CH₃,—(CH₂)_(n)—CH(CF₃)₂—O—C(O)—O—C(CH₃)₃, —(CH₂)_(n)—C(CF₃)₂—OH,—(CH₂)_(n)C(O)NH₂, —(CH₂)_(n)C(O)Cl, —(CH₂)_(n)C(O)OR⁵, —(CH₂)_(n)—OR⁵,—(CH₂)_(n)—OC(O)R⁵, —(CH₂)_(n)—C(O)R⁵,—(CH₂)_(n)—OC(O)OR⁵—(CH₂)_(n)Si(R⁵)₃, —(CH₂)_(n)Si(OR⁵)₃,—(CH₂)_(n)—O—Si(R⁵)₃ and —(CH₂)C(O)OR⁶ wherein n independentlyrepresents an integer from 0 to 10 and R⁵ independently representshydrogen, linear or branched C₁–C₂₀ alkyl, linear or branched C₁–C₂₀halogenated or perhalogenated alkyl, linear or branched C₂–C₁₀ alkenyl,linear or branched C₂–C₁₀ alkynyl, C₅–C₁₂ cycloalkyl, C₆–C₁₄ aryl,C₆–C₁₄ halogenated or perhalogenated aryl, and C₇–C₂₄ aralkyl.Representative hydrocarbon groups set forth under the definition of R⁵are the same as those identified above under the definition of R¹ to R⁴.As set forth above under R¹ to R⁴ the hydrocarbon groups defined underR⁵ may be halogenated and perhalogenated. For example, when R⁵ is C₁–C₂₀halogenated or perhalogenated alkyl, R⁵ may be represented by theformula C_(z)W″_(2z+1), wherein z and W″ are defined as above and atleast one W″ on the alkyl group is a halogen. It is to be recognizedthat when the alkyl group is perhalogenated, all W″ substituents arehalogenated. Examples of perhalogenated alkyl groups include, but are byno means limited to, trifluoromethyl, trichloromethyl, —C₇F₁₅, and—C₁₁F₂₃. Examples of perhalogenated aryl groups include, but are by nomeans limited to, pentachlorophenyl and pentafluorophenyl. The R⁶radical represents an acid labile moiety selected from —C(CH₃)₃,—Si(CH₃)₃, —CH(R⁷)OCH₂CH₃, —CH(R⁷)OC(CH₃)₃ or the following cyclicgroups:

wherein R⁷ represents hydrogen or a linear or branched (C₁–C₅) alkylgroup. The alkyl groups may include methyl, ethyl, propyl, i-propyl,butyl, i-butyl, t-butyl, pentyl, t-pentyl and neopentyl. In the abovestructures, the single bond line projecting from the cyclic groupsindicates the position where the cyclic protecting group is bonded tothe acid substituent. Examples of R⁶ radicals include1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2-isobornyl,2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl,3-oxocyclohexanonyl, mevalonic lactonyl, 1-ethoxyethyl and 1-t-butoxyethyl.

The R⁶ radical can also represent dicyclopropylmethyl (Dcpm), anddimethylcyclopropylmethyl (Dmcp) groups which are represented by thefollowing structures:

In the structure (B) above, R¹ and R⁴ together with the two ring carbonatoms to which they are attached may represent a substituted orunsubstituted cycloaliphatic group containing 4 to 30 ring carbon atoms,a substituted or unsubstituted aryl group containing 6 to 18 ring carbonatoms, or a combination thereof. The cycloaliphatic group can bemonocyclic or polycyclic. When unsaturated, the cyclic group may containmonounsaturation or multiunsaturation. In one embodiment, theunsaturated cyclic group may be a monounsaturated cyclic group. Whensubstituted, the rings may contain monosubstitution ormultisubstitution, wherein the substituents may independently beselected from hydrogen, linear or branched C₁–C₅ alkyl, linear orbranched C₁–C₅ haloalkyl, linear or branched C₁–C₅ alkoxy, halogen andcombinations thereof. R¹ and R⁴ may be taken together to form thedivalent bridging group, —C(O)-Q-(O)C—, which when taken together withthe two ring carbon atoms to which they are attached form a pentacyclicring, wherein Q represents an oxygen atom or the group N(R⁸), and R⁸ maybe selected from hydrogen, halogen, linear or branched C₁–C₁₀ alkyl, andC₆–C₁₈ aryl. A representative structure is shown in below as Structure(C):

wherein each W′″ is independently defined as above and m is an integerfrom 0 to 5.

Deuterium enriched norbornene-type monomers wherein at least one of thehydrogen atoms on the norbornene-type moiety and/or one at least one ofthe hydrogen atoms on a pendant hydrocarbon group described under R¹ toR⁴ have been replaced by a deuterium atom are contemplated within thescope of the present invention. In one embodiment, at least 40 percentof the hydrogen atoms on the norbornene-type moiety and/or thehydrocarbon group are replaced by deuterium. In another embodiment, atleast about 50 percent of the hydrogen atoms on the norbornene-typemoiety and/or the hydrocarbon group are replaced by deuterium. In yetanother embodiment, at least about 60 percent of the hydrogen atoms onthe norbornene-type moiety and/or the hydrocarbon group are replaced bydeuterium. In one embodiment, the deuterated monomers are represented byStructure (D) below:

wherein W′″ is defined as above, R^(D) is deuterium, “i” is an integerfrom 0 to 6, R¹ and R² independently represent a hydrocarbyl orfunctional substituent as defined above and R^(1D) and R^(2D) may or maynot be present and independently represent a deuterium atom or adeuterium enriched hydrocarbon group containing at least one deuteriumatom; with the proviso that when “i” is 0, at least one of R^(1D) andR^(2D) must be present. In one embodiment, the deuterated hydrocarbongroup is selected from linear or branched C₁–C₁₀ alkyl wherein at least40 percent of the hydrogen atoms on the carbon backbone are replaced bydeuterium. In another embodiment, the deuterated hydrocarbon group isselected from linear or branched C₁–C₁₀ alkyl wherein at least 50percent of the hydrogen atoms on the carbon backbone are replaced bydeuterium. In yet another embodiment, the deuterated hydrocarbon groupis selected from linear or branched C₁–C₁₀ alkyl wherein at least 60percent of the hydrogen atoms on the carbon backbone are replaced bydeuterium.

A further illustrative list of norbornene-type monomers is shown below:

A still further illustrative list of norbornene-type monomers of thepresent invention includes: bicyclo[2.2.1] hept-5-ene-2-carboxylic acid5-oxo-4-oxa-tricyclo[4.2.1.03,7]non-2-yl ester, bicyclo[2.2.1]hept-5-ene-2-carboxylic acid 2-methoxy-ethyl ester, bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, bicyclo[2.2.1] hept-5-ene-2-carboxylicacid 2-oxo-tetrahydro-furan-3-yl ester,4-Oxa-tricyclo[5.2.1.02,6]dec-8-ene-3,5-dione,4-Oxa-tricyclo[5.2.1.02,6]dec-8-ene-3-one, 1,4,4a,5,6,7,8,8a-Octahydro-1,4-methano-naphthalen-5-ol, 2-bicyclo[2.2.1]hept-5-en-2-yl-propan-2-ol,2-bicyclo[2.2.1]hept-5-en-2-ylmethyl-1,1,1,3,3,3-hexafluoro-propan-2-ol,2-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid 1,1,2-trimethyl-propylester, 2-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid tert-butyl ester,2-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid 2-ethyl-adamantan-2-ylester, 2-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid2-methyl-adamantan-2-yl ester, 2-bicyclo[2.2.1]hept-5-ene-2-carboxylicacid 1 ,2,3,3-tetramethyl-bicyclo[2.2.1]hept-2-yl ester, and2-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid 2-hydroxy-ethyl ester.

Multi-ethylenically unsaturated monomers of the present invention may beincorporated into the addition polymer of the present invention toprovide crosslinking either during polymerization, or subsequent topolymerization, or both. Multi-ethylenically unsaturated monomers may bepolar olefinic or non-polar olefinic monomers, and the ethylenicallyunsaturated groups may be identical or different. Useful (meth)acrylicmulti-ethylenically unsaturated monomers include, but are not limitedto, allyl (meth)acrylate, diallyl phthalate, 1,4-butylene glycoldi(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and1,1,1-trimethylolpropane tri(methyl)acrylate. Useful non-polar olefinssuitable as crosslinkers may be any multi-ethylenically unsaturatednon-polar olefin capable of incorporation into more than one polymerchain of the addition polymer of the present invention, including, forexample: α,ω-alkadienes, such as 1,5-hexadiene; other non-conjugatedalkadienes such as 1,4-hexadiene; and non-polar olefinic monomerscontaining three or more carbon-carbon double bonds.

Crosslinked polymers can be prepared by copolymerizing thenorbornene-type monomer(s) set forth under Structure (B) above with amultifunctional norbornene-type crosslinking monomer(s). Bymultifunctional norbornene-type crosslinking monomer is meant that thecrosslinking monomer contains at least two norbornene-type moieties(norbornene-type double bonds), each functionality being polymerizablein the presence of the catalyst system of the present invention. Thecrosslinkable monomers include fused multicyclic ring systems and linkedmulticyclic ring systems. Examples of fused crosslinking agents areillustrated in structures below. For brevity, norbornadiene is includedas a fused multicyclic crosslinking agent and is considered to containtwo polymerizable norbornene-type double bonds.

wherein Y represents a methylene (—CH₂—) group and m independentlyrepresents an integer from 0 to 5, and when m is 0, Y represents asingle bond. Representative monomers under the forgoing formulae aredisclosed by, for example, Bell et al. in U.S. Pat. No. 6,350,832.

Hydrocarbon groups, R, include, for example, hydrogen, linear andbranched C₁–C₂₀ alkyl, C₅–C₁₀ cycloalkyl, linear and branched C₂–C₂₀alkenyl, C₆–C₁₅ cycloalkenyl, allylic ligands or canonical formsthereof, C₆–C₃₀ aryl, C₆–C₃₀ heteroatom containing aryl and C₇–C₃₀aralkyl; each of the foregoing groups can optionally be substituted withhydrocarbyl and/or heteroatom substituents selected from linear orbranched C₁–C₅ alkyl, linear or branched C₁–C₅ haloalkyl, linear orbranched C₂–C₅ alkenyl and haloalkenyl, halogen, sulfur, oxygen,nitrogen, phosphorus, and phenyl optionally substituted with linear orbranched C₁–C₅ alkyl, linear or branched C₁–C₅ haloalkyl, and halogen;wherein the cycloalkyl and cycloalkenyl groups may be monocyclic ormulticyclic; wherein the aryl groups can be a single ring (e.g., phenyl)or a fused ring system (e.g., naphthyl); wherein the cycloalkyl,cycloalkenyl and aryl groups can be taken together to form a fused ringsystem; and wherein each of the monocyclic, multicyclic and aryl ringsystems may optionally be monosubstituted or multisubstituted with asubstituent independently selected from hydrogen, linear and branchedC₁–C₅ alkyl, linear and branched C₁–C₅ haloalkyl, linear and branchedC₁–C₅ alkoxy, chlorine, fluorine, iodine, bromine, C₅–C₁₀ cycloalkyl,C₆–C₁₅ cycloalkenyl and C₆–C₃₀ aryl.

In the method of polymerizing of the present invention, the cationicmetal-pair complex can be used to polymerize: one or more “non-polarolefinic monomers”; one or more “polar olefinic monomers”; orcombinations of one or more non-polar olefinic monomers and one or morepolar olefinic monomers to form the addition polymer of the presentinvention. The number average molecular weight, Mn, of the additionpolymer of the present invention is: at least 500, at least 1,000, atleast 10,000, or at least 20,000; and no more than 5,000,000, no morethan 1,000,000, no more than 500,000, or no more than 200,000. Thepolydispersity of the MWD of the addition polymer of the presentinvention is: at least 1.000, at least 1.001, at least 1.01, or at least1.05; and no more than 10, no more than 2.5, no more than 1.5, or nomore than 1.1. The MWD of the addition polymer of the present inventionmay be unimodal or multi-modal, wherein multi-modal includes bimodal andtrimodal, as well as higher degrees of modality, and wherein thepolydispersity of the MWD for each mode may have the upper and lowerlimits defined supra.

The “poly(non-polar olefin)” of the present invention is any polymerthat can be made from any of the non-polar olefinic monomers of thepresent invention. The following is a short, non-exhaustive, list ofillustrative examples poly(non-polar olefin)s, which may be homopolymersor copolymers: polyethylene, polypropylene, ethylene-propylenecopolymers, ethylene-propylene-(non-conjugated diene monomer) (“EPDM”)copolymers, LLDPE, polystyrene homo- and copolymers, polybutadiene homo-and copolymers, and polynorbornene. In fact, the poly(non-polar olefin)may include, as polymerized units, any non-polar olefin capable ofinsertion addition polymerization in the presence of the cationicmetal-pair complex of the present invention.

The “poly(polar olefin)” of the present invention is any polymer thatcan be made from the polar olefinic monomers of the present invention.The following is short, non-exhaustive, list of illustrative examplespoly(polar olefin)s, which may be homopolymers or copolymers:poly[(meth)acrylates] such as poly(methyl methacrylate), poly(butylacrylate-co-methyl methacrylate), poly[vinylidene halide(s)], poly(vinylacetate), and poly(vinyl ether). In fact, the poly(polar olefin) mayinclude, as polymerized units, any polar olefin capable of insertionaddition polymerization in the presence of the cationic metal-paircomplex of the present invention.

A “poly[(polar olefin)-(non-polar olefin)]” of the present invention isany polymer that can be made from at least one of the non-polar olefinicmonomers and at least one of the polar olefinic monomers of the presentinvention. The following is short, non-exhaustive, list of illustrativeexamples of poly[(polar olefin)-(non-polar olefin)] copolymers:poly[ethylene-co-methyl (meth)acrylate], poly[octene-co-methyl(meth)acrylate], poly[propylene-co-(meth)acrylate],poly[norbornene-co-(meth)acrylate]. In fact, the poly[(polarolefin)-(non-polar olefin)] may include, as polymerized units, any polarolefin and any non-polar olefin capable of insertion additionpolymerization in the presence of the cationic metal-pair complex of thepresent invention. The molar ratio of polar olefinic monomers tonon-polar olefinic monomers, present as polymerized units in thepoly[(polar olefin)-(non-polar olefin)] of the present invention is: atleast 0.05:99.95, at least 0.5:99.5, at least 10:90, at least 20:80, orat least 40:60; or no more than 99.95:0.05, no more than 99.5:0.5, nomore than 90:10, no more than 80:20, or no more than 60:40.

When the addition polymer of the present invention is a copolymer, thatcopolymer may include, as polymerized units, two, three, four, or morethan four different monomers, with no particular limit to the number ofdifferent monomers. For example, in one embodiment of the presentinvention, the poly[(polar olefin)-(non-polar olefin)] is a terpolymerincluding, as polymerized units, norbornene, 1-octene, and methylacrylate.

When at least one polar monomer polymerized by the method of the presentinvention to form a “poly[(polar olefin)-(non-polar olefin)]” is a(meth)acrylate monomer, the molar ratio of (meth)acrylate monomers tonon-polar olefinic monomers, present as polymerized units in thepoly[(polar olefin)-(non-polar olefin)] of the present invention is: atleast 0.05:99.95, at least 0.5:99.5, at least 10:90, at least 20:80, orat least 40:60; or no more than 99.95:0.05, no more than 99.5:0.5, nomore than 90:10, no more than 80:20, or no more than 60:40.

Further, when both polar olefinic monomers and non-polar olefinicmonomers are polymerized together in the polymerization method of thepresent invention, the molar percentage of monomer incorporated intopoly[(polar olefin)-(non-polar olefin)], based on total moles of monomerincorporated into all polymer produced in the polymerization, is: atleast 70, at least 80, at least 90 or at least 95; no more than 100, nomore than 99, no more than 97.

In particular, when both polar olefinic monomers and non-polar olefinicmonomers are polymerized together in the polymerization method of thepresent invention, and at least one of the polar olefinic monomers is a(meth)acrylate monomer, the molar percentage of monomer incorporatedinto poly[(polar olefin)-(non-polar olefin)], based on total moles ofmonomer incorporated into all polymer produced in the polymerization,is: at least 70, at least 80, at least 90 or at least 95; no more than100, no more than 99, no more than 97.

Still further, when the addition polymer of the present invention is apoly(polar olefin) and at least one of the polar olefinic monomers,incorporated as polymerized units, is a (meth)acrylate monomer, themolar ratio of all (meth)acrylate monomers, present as polymerizedunits, to all non-(meth)acrylate monomers, present as polymerized units,is: at least 0.05:99.95, at least 0.5:99.5, at least 10:90, at least20:80, or at least 40:60; or no more than 100:0, no more than 99.5:0.5,no more than 90:10, no more than 80:20, or no more than 60:40.

Similarly, when the addition polymer of the present invention is apoly[(polar olefin)-(non-polar olefin)] and at least one of the polarolefinic monomers, incorporated as polymerized units, is a(meth)acrylate monomer, the molar ratio of all (meth)acrylate monomers,present as polymerized units, to all non-(meth)acrylate monomers,present as polymerized units, is: at least at least 0.05:99.95, at least0.5:99.5, at least 10:90, at least 20:80, or at least 40:60; or no morethan 99.95:0.05, no more than 99.5:0.5, no more than 90:10, no more than80:20, or no more than 60:40.

When the addition polymer of the present invention includes, aspolymerized units, at least one cyclic olefin, incorporated aspolymerized units, the molar ratio of all cyclic olefin monomers,present as polymerized units, to all non-(cyclic olefin) monomers,present as polymerized units, is: at least 0.05:99.95, at least0.5:99.5, at least 10:90, at least 20:80, or at least 40:60; or no morethan 100:0, no more than 99.5:0.5, no more than 90:10, no more than80:20, or no more than 60:40.

Crosslinked polymers can be prepared by copolymerizing thenorbornene-type monomer(s) set forth under Structure (B) above with amultifunctional norbornene-type crosslinking monomer(s). Bymultifunctional norbornene-type crosslinking monomer is meant that thecrosslinking monomer contains at least two norbornene-type moieties(norbornene-type double bonds), each functionality being polymerizablein the presence of the catalyst system or the present invention. Thecrosslinkable monomers include fused multicyclic ring systems and linkedmulticyclic ring systems. Examples of fused crosslinking agents areillustrated in structures below. For brevity, norbornadiene is includedas a fused multicyclic crosslinking agent and is considered to containtwo polymerizable norbornene-type double bonds.

wherein Y represents a methylene (—CH₂—) group and m independentlyrepresents an integer from 0 to 5, and when m is 0, Y represents asingle bond. Representative monomers under the forgoing formulae aredisclosed by, for example, Bell et al. in U.S. Pat. No. 6,350,832.

Hydrocarbon groups, R, suitable for use with the present inventioninclude, for example, hydrogen, linear and branched C1–C20 alkyl, C5–C10cycloalkyl, linear and branched C2–C20 alkenyl, C6–C15 cycloalkenyl,allylic ligands or canonical forms thereof, C6–C30 aryl, C6–C30heteroatom containing aryl and C7–C30 aralkyl; each of the foregoinggroups can optionally be substituted with hydrocarbyl and/or heteroatomsubstituents selected from linear or branched C1–C5 alkyl, linear orbranched C₁–C5 haloalkyl, linear or branched C2–C5 alkenyl andhaloalkenyl, halogen, sulfur, oxygen, nitrogen, phosphorus, and phenyloptionally substituted with linear or branched C1–C5 alkyl, linear orbranched C1–C5 haloalkyl, and halogen; wherein the cycloalkyl andcycloalkenyl groups may be monocyclic or multicyclic; wherein the arylgroups can be a single ring (e.g., phenyl) or a fused ring system (e.g.,naphthyl); wherein the cycloalkyl, cycloalkenyl and aryl groups can betaken together to form a fused ring system; and wherein each of themonocyclic, multicyclic and aryl ring systems may optionally bemonosubstituted or multisubstituted with a substituent independentlyselected from hydrogen, linear and branched C1–C5 alkyl, linear andbranched C1–C5 haloalkyl, linear and branched C1–C5 alkoxy, chlorine,fluorine, iodine, bromine, C5–C10 cycloalkyl, C6–C15 cycloalkenyl andC6–C30 aryl.

The method of preparing the addition polymer of the present inventioncan be carried out at a reaction temperature (° C.) of: at least −100°C., at least −50° C., at least 0° C., or at least 20° C.; and no morethan 200° C., no more than 160° C., no more than 140° C., or no morethan 120° C. This method can be carried out at a pressure (inatmospheres, i.e., the pressure inside the reactor is 1.0 atmosphere fora value of 1.0) of: at least 0.01, at least 0.1, at least 0.5, or atleast 1.0, and no more than 1,000, no more than 100, no more than 10, orno more than 5. Further, the molar ratio of ethylenically unsaturatedmonomer to the cationic metal-pair complex of present invention is: atleast 50:1, at least 200:1, at least 250:1, or at least 1,000:1, and nomore than 5,000,000:1, no more than 2,000,000:1, or no more than500,000:1, no more than 250,000:1, or no more than 100,000:1. Forgaseous monomers at high pressures, in particular constant highpressures, e.g., equal to or greater than 400 psi, the molar ratio ofethylenically unsaturated monomer to the cationic metal-pair complex ofpresent invention may be even higher than 5,000,000:1, for example, nomore than 6,000,000:1, no more than 8,000,000:1, or even higher. In themethod of polymerization of the present invention, the amount ofdiluent, expressed as volume (milliliters) of diluent per millimole ofthe cationic metal-pair complex of the present invention, is: at least0.0, at least 10, at least 50, or at least 100; and no more than10,000,000, no more than 1,000,000, no more than 100,000, no more than10,000, or no more than 5,000.

When particles of the addition polymer are produced by the method ofpreparing the addition polymer of the present invention, depending onthe particular details of that method, the polymer particles have a meanparticle diameter (i.e., mean particle size), expressed in microns, of:at least 0.002, at least 0.04, at least 0.1, or at least 0.8; and nomore than 500, no more than 20, no more than 10, no more than 5, or nomore than 3. The PSD polydispersity of the particles is: at least 1, atleast 1.001, at least 1.01, or at least 1.05; and no more than 10, nomore than 5, no more than 1, no more than 1.3, or no more than 1.1. ThePSD of the addition polymer of the present invention may be unimodal ormulti-modal, wherein multi-modal includes bimodal and trimodal,tetramodal, as well as higher degrees of modality, and wherein thepolydispersity of the, PSD for each particle size mode may have theupper and lower limits defined supra. One skilled in the art ofcatalytic polymerization will further recognize that it is even possibleto prepare particles having a mean particle diameter greater than 1000microns (1 millimeter). This may happen, for example, as the result ofevaporation during or after solution or bulk polymerization, orpolymerization involving polymer precipitation. In this way, even largermonolithic polymer structures may be formed.

The method for preparing the addition polymer of the present inventionmay be carried out in bulk or in a diluent. If the catalytic compositionis soluble in the one or more ethylenically unsaturated monomers to bepolymerized, it may be convenient to carry out the polymerization inbulk. Such bulk polymerizations may be carried out, for example, inbatch or continuous mode, or by reaction injection molding or other moldbased techniques. In another embodiment of the present invention, thepolymerization is carried out in a diluent. Any organic or aqueousdiluent which does not adversely interfere with the catalyticcomposition and is a solvent for the monomers may be employed.Illustrative examples of organic solvents are: aliphatic (non-polar)hydrocarbons, e.g., hexane and heptane; alicyclic hydrocarbons, e.g.,cyclohexane; aromatic hydrocarbons, e.g., toluene; halogenated (polar)hydrocarbons, e.g., methylene chloride and chlorobenzene. Forpolymerization systems in which the catalytic composition is notdegraded, the diluent may be water, solvents miscible with water, andcombinations thereof. The diluent may further include, for example, anyof the fugitive substances disclosed in U.S. Pat. No. 6,632,531, e.g.,2,2-dimethylypropane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethylenepropane (−42.1° C.), carbon dioxide, and tetrafluoromethane (−130° C.),wherein the reaction is carried out under supercritical or belowsupercritical conditions.

The suitability of a given atmosphere for carrying out any of thereactions of the present invention will depend upon the stability of thereactants, intermediates and by-products to that atmosphere. Typicallygases, including nitrogen or argon, for example, are utilized. Choice ofatmosphere gases for a given polymerization will be apparent to one ofordinary skill in the art.

The diluent of the present invention may also be an “ionic liquid”.Ionic liquids are either organic salts or mixtures of salts that arefluid at room or near-room temperature (see: Dupont, J. Chem. Rev. 2002,102, 3667; Kabisa, P. Prog. Poly. Sci. 2004, 29, 3). A property of ionicliquids is their zero vapor pressure, making them potential solvents forzero-(volatile organic) chemical processes and possible alternative forsupercritical CO₂. Ionic liquids are, for example, composed of bulky1,3-dialkylimidazolium, alkylammonium, alkylphosphonium oralkylpyridinium organic cations and inorganic anions such as mostfrequently AlCl₄ ⁻, BF₄ ⁻ or PF₆ but also NO₃, ClO₄, CF₃COO₂, CF₃SO₃ orCH₃COO₂ and other anions. The most commonly used neutral ionic liquidsinclude 1-butyl-3-methylimidazolium hexafluorophospate ortetrafluoroborate abbreviated as [bmim][PF6] and [bmim][BF4]correspondingly.

typical cationiccomponents ofionic liquids:

typical anioniccomponents ofionic liquids:

When utilized in the preparation of the addition polymer of the presentinvention, the monomers and/or catalytic composition of the presentinvention may not be fully soluble, or may even be insoluble, in thediluent. This situation might, for example, occur in heterogeneoussystems wherein the locus of polymerization must be accessed by bothcatalytic composition and ethylenically unsaturated monomer. In suchcases, it may be advantageous to employ one or more transport agents totransport monomers, or the complexes of the catalytic composition, tothe desired locus of polymerization. For example, transport agents suchas cyclodextrins may be advantageously employed to transportethylenically unsaturated monomers having low, or very low, watersolubility, across the aqueous phase to polymer particles during aqueousemulsion polymerization.

In addition to being carried out as bulk and solution polymerizations,the polymerizations of the present reaction can be carried out in thegas phase in, for example fluidized bed or stirred tank reactors,optionally in the presence of prepolymer for control of the size andshape of polymers formed. Polyethylene, polybutene, polyhexene, andrelated copolymers, including copolymers containing, for example, methylmethacrylate may be prepared by gas phase polymerization.

A still further method for producing the addition polymer of the presentinvention may be any appropriate method known to the art, including, butnot limited to aqueous solution polymerization, emulsion polymerization,suspension polymerization, microemulsion polymerization, mini-emulsion,and slurry polymerization. Descriptions of emulsion polymerizationmethods are disclosed in Blackley, D. C. Emulsion Polymerisation;Applied Science Publishers: London, 1975; Odian, G. Principles ofPolymerization; John Wiley & Sons: New York, 1991; EmulsionPolymerization of Acrylic Monomers; Rohm and Haas, 1967. The method ofthe present invention further includes methods disclosed in U.S. Pat.No. 6,632,531, and published U.S. patent application US2003/0007990.

The cationic metal-pair complex of the present invention is suitablyemployed as an unsupported material. Alternatively, any of the complexesof the present invention may be supported on an “inorganic solidcarrier” (“inorganic carrier”) or an “organic polymeric solid catalystcarrier” (“organic carrier”) which is normally solid under reactionconditions and is heterogeneous, i.e., is substantially insoluble in thereaction medium. Used herein, the terms “carrier” and “support” are usedinterchangeably. Illustrative of suitable inorganic carriers areinorganic acidic oxides such as alumina and inorganic materials known asrefractory oxides. Suitable refractory oxides include syntheticcomponents as well as acid treated clays and similar materials such askieselguhr or crystalline macroreticular aluminosilicates known in theart as molecular sieves. In general, synthetic catalyst carriers arepreferred over natural occurring materials or molecular sieves.Exemplary synthetic catalyst carriers include alumina, silica-alumina,silica-magnesia, silica-alumina-titania, silica-alumina-zirconia,silica-titania-zirconia, silica-magnesia- alumina, magnesium chloride,and the like. Organic carriers include, for example, macroreticularresins which may, or may not, bear polar functional groups orcarbon-carbon double bonds.

When the cationic metal-pair complex of the present invention issupported, its proportion to carrier is not critical. In general,proportions of cationic metal-pair complex, or precursor complex of thepresent invention, in percent by weight, based on the catalyst carrier,are: at least 0.001%, at least 0.01%, at least 0.1%, or at least 1.0%;and no more than 5%, no more than 10%, no more than 20%, or no more than70%. The cationic metal-pair complex is introduced onto the carrier inany suitable manner. In one modification, the supported cationicmetal-pair complex is prepared by intimately contacting the preformedcationic metal-pair complex and the carrier in an inert diluent, whichmay or may not be the same inert diluent employed for preparing thecationic metal-pair complex. In another modification, the cationicmetal-pair complex can be prepared directly on the catalyst carriersupport surface by contacting the cationic metal-pair complex precursorsin the presence of the catalyst carrier in a suitable inert diluent. Inaddition to the supports enumerated supra, the cationic metal-paircomplex of the present invention can be supported on any of the supportsor matrices disclosed in published U.S. patent applicationsUS2002/60226997, US2002/0052536, in U.S. patent applications Ser. No.60/383650 and Ser. No. 60/440142., and in Chen and Marks, Chem. Rev.,2000 100 1391–1434.

One skilled in the art will recognize that, when aqueous emulsionpolymerization and microemulsion polymerization are used to prepare theaddition polymer of the present invention, surfactants will, optionally,be present in the reaction medium. Conventional surfactants may be usedto stabilize the emulsion polymerization systems before, during, andafter polymerization of monomers. For emulsion polymers, theseconventional surfactants will usually be present at levels of 0.1percent to 6 percent by weight based on the weight of total monomer,whereas microemulsion polymerizations may require level as high as 30weight %. Useful surfactants include,: anionic surfactants, for example,sodium lauryl sulfate and sodium dodecyl benzene sulfonate; nonionicsurfactants, for example, glycerol aliphatic esters and polyoxyethylenealiphatic esters; and amphoteric surfactants, for example,aminocarboxylic acids, imidazoline derivatives, and betaines.

Methods for generating cationic mono-metallic complexes by treatingtheir neutral precursors with stoichiometric (i.e., one equivalent permetal atom) or excess amounts of activator component are disclosed inChen, E. Y.-X.; Marks, T. J. Chem. Rev. 2000 100, 1391 and Mecking, S.Coord. Chem. Rev. 2000 203 325.

In the method of preparing the catalytic composition of the presentinvention, a cationic metal-pair complex is generated by treating aprecursor complex using amounts of activator component suitable toremove leaving group Y. The leaving group Y is replaced with at leastone replacement moiety in an amount sufficient to at least fill anycoordination sites, of metal atoms M¹ and M², vacated by the removal ofsaid leaving group Y, to form said cationic metal-pair complex.

The precursor complex from which the leaving group Y is removed may be afull-(metal pair) complex or a first semi-(metal pair) complex. When theprecursor is a first semi-(metal pair) complex, the leaving group Y isreplaced by a second semi-(metal pair) complex. The temperature (° C.)for the reaction generating the cationic metal-pair complex is: at least−100° C., at least −50° C., at least 0° C., or at least 20° C.; and nomore than 200° C., no more than 160° C., no more than 140° C., or nomore than 120° C. In the method of preparation of the cationicmetal-pair complex of the present invention, the amount of diluent,expressed as volume (milliliters) pre millimole of cationic metal-paircomplex, is: at least 0.0, at least 2, at least 5, or at least 10; andno more than 1,000, no more than 500, no more than 200, or no more than100. Useful diluents include any of the non-aqueous diluents (videsupra) useful in carrying out the polymerization of the ethylenicallyunsaturated monomers of the present invention. In cases in which neitherthe precursor complex nor the cationic metal-pair complex is adverselyaffected, water or water miscible diluents may be utilized as well.

In one embodiment of the method of the present invention for preparing,from a full-(metal-pair) precursor complex, a cationic metal-paircomplex, the removal of leaving group Y is represented by the followingreaction scheme:

wherein the activator component is MAO or modified MAO.

In another embodiment of the method of the present invention, thecationic metal-pair complex is formed by: oxidative cleavage of the bondbetween first metal atom, M¹, and a leaving group Y and of the bondbetween second metal atom, M², and that leaving group Y of afull-(metal-pair) precursor complex. This embodiment is represented bythe following reaction scheme:

wherein the activator component is Z⁺WCA⁻ and Z⁺ may be, for example,Ag⁺ or Cp₂Fe⁺. Used herein, “Cp” denotes “cyclopentadienyl”, and Cp₂Fe⁺denotes the “ferricenium ion”.

In a further embodiment of the method of the present invention, thecationic metal-pair complex is formed by: abstractive cleavage of thebond between first metal atom, M¹, and the leaving group Y, and of thebond between second metal atom, M², and the leaving group Y of afull-(metal-pair) precursor complex. This embodiment is represented bythe following reaction scheme:

wherein the activator component is, for example, Ph₃C⁺WCA⁻. Used hereinPh₃C⁺ is the “trityl cation”, also denoted “triphenyl carbocation”.

In a still further embodiment of the method of the present invention,the cationic metal-pair complex is formed by protonolysis of the bondbetween first metal atom, M¹, and the leaving group Y, and of the bondbetween second metal atom, M², and the leaving group Y of afull-(metal-pair) precursor complex. This embodiment is represented bythe following reaction scheme:

wherein, for example, Z is: NR_(j)Ar_(k) (wherein R is a methyl or otheralkyl group; Ar is a phenyl or other aryl group); (OEt₂)₂; first orsecond labile ligand; some other labile neutral electron donor ligandthat is present, but does not become part of the cationic metal-paircomplex.

In yet another embodiment of the method-of the present invention, thecationic metal-pair complex is formed by abstraction by a neutral Lewisacid of leaving group Y of a full-(metal-pair) precursor complex. Thisembodiment is represented by the following reaction scheme:

wherein Z is the Lewis acid and, for example, Z=B(C₆F₅)₃ or otherB(Ar^(F))₃ compounds. “Ar^(F)” denotes “fluoroaryl”, and “YZ⁻” serves asweakly coordinating anion, WCA⁻.

In another embodiment of the method of the present invention, thecationic metal-pair complex is formed by abstraction by silver, thalliumor alkali metal salts of leaving group Y of a full-(metal-pair)precursor complex. This embodiment is represented by the followingreaction scheme:

wherein, for example, Z=Ag, Tl, Li, Na, K, or Cs.

In another embodiment of the method of the present invention, a firstsemi-(metal pair) precursor complex is combined with any of the aboveactivator components, (e.g., silver salt) to remove leaving group Y, andleaving group Y is replaced by a second semi-(metal pair) precursorcomplex during or after the removal of leaving group Y from the firstsemi-(metal pair) complex. It is understood for the equations of thisparagraph, and the paragraph immediately following, that bridging moietyL³ is derived from a first ligand or first anionic hydrocarbyl radicalof a precursor complex, or a second ligand or a second anionichydrocarbyl radical of a precursor complex. For example, a second ligand(i.e., a ligand of the set L²), already bonded to M² and capable offorming a coordination bond with M¹, becomes a third ligand (i.e., aligand of the set L³) upon formation of that coordination bond with M¹.The weakly coordinating anion, WCA⁻, may be formed, for example, by thecombining of the activator with Y, or by the displacement of Y⁻ with acationic moiety of an ionic activator, with the anionic moiety of thatactivator remaining as WCA⁻,

A non-exhaustive list of additional schemes of generation of thecationic metal-pair complex of the present invention includes:

When L³ or L³⁻ appears over an arrow in an above equations, it will beunderstood that L³ or L³⁻represents a ligand capable of forming at leastone coordination bond with each of M¹ and M², and which, upon formationof at least one coordination bond to each of M¹ and M², will become athird ligand (bridging moiety) of the set L³.

The following is an example of the reaction using ZL^(3′) (immediatelyabove):

In another embodiment of the method of preparing the cationic metal-paircomplex of the present invention, any of the preceding reaction schemesmay be carried out in the presence of an inorganic support, an organicpolymeric support, a pair-coupling moiety, or a combination thereof.Within this embodiment, a non-exhaustive list of ways in which a supportor pair-coupling moiety may be utilized includes: combination with aprecursor complex, followed by addition of an activator component;combination with of an activator component, followed by addition of aprecursor component; when a first semi-(metal pair) precursor complex isinvolved and the first semi-(metal pair) precursor complex is notalready associated with a support, combining the first semi-(metal pair)precursor complex with a support and then reacting it with the secondsemi-(metal pair) precursor complex, or combining the first semi-(metalpair) precursor complex with a supported second semi-(metal pair)precursor complex; or combining the cationic metal-pair complex and asupport.

The addition polymers prepared using the catalytic composition of thepresent invention afford many new products and market opportunitiescurrently unachievable. Applications for the polymers include polymersuseful in preparation of photoresists, polymers useful in electronics,polymers useful in computer components and microcomponents, polymersuseful as plastics additives (e.g., heat distortion temperatureimprovers, impact modifiers, and processing aids), UV stablethermoplastic elastomers, colorable (including dyeable) polyolefinplastics and other polymers, and new low-cost, high melting point,optical polymers. The polymers of the present invention include polymersthat, while having polyolefin type attributes, are also paintable, orotherwise coatable without recourse to pretreatment which adds expenseand often creates environmental hazard. Applications further includepaint binders that can undergo film formation in the absence ofcoalescents while still providing paints that are both durable anddirt-resistant, enabling productions of, for example, aqueous and powderformulations having reduced or zero concentrations of volatile organiccompounds (VOCs) without sacrificing paint properties. Polymers selectedfrom those of the present invention may be the principal, sole, or minorcomponents of coatings (paints, stains, varnishes, adhesives andmastics) for essentially any substrate, including non-polar and polarthermoplastics, thermoset plastics, other organic and inorganicpolymers, glass, stone, ceramic, wood, particle board, paper, leather,concrete, asphalt, cement, and metal. Whether the polymers of thepresent invention are included in the coating, the substrate, or both,the resulting coated substrates can, for example, be decorative and/orof enhanced durability, attributes that are highly desirable in, forexample, vehicular, appliance, architectural, household, device housing(including electronic), decorative design, and ornamental applications.

Polymers of the present invention are further useful as ionomers forapplications requiring extreme toughness (e.g., golf ball covers) orsuperior sealing properties (e.g., bacon packaging). They find furtherutility as thermoplastics, as thermosets, and as compatibilizers,affording compatible blends of non-polar and polar polymers withenhanced properties compared with the component polymers. They findstill further utility as impact and processing enhancing additives forthermoplastic and thermoset resins. When functionalized appropriately,these polymers behave as colorants, UV and other radiation absorbers,and photosensitizers. When combined with active ingredients of varioustypes, they can enable delivery of those ingredients to targeted loci.Such active ingredients include, pharmaceutical, pesticides, otherbiologically active substances, colorants and other optically activesubstances, and analytical tags,

The polymers of the present invention are useful inter alia inelectronic and optical applications. They are useful as components inresist materials utilized in the manufacture of integrated circuits(ICs). The patterning of IC's is carried out according to variouslithography techniques known in the art. Polymers of the presentinvention that contain acid labile groups pendant from the backbone canbe used in radiation sensitive photoresist compositions. (J. V. Crivelloet al., Chemically Amplified Electron-Beam Photoresists, Chem. Mater.1996 8 376–381). Electronic applications further include, but are notlimited to, dielectric films (i.e., multichip modules and flexiblecircuits), chip attach adhesives, underfill adhesives, chipencapsulants, glob tops, near hermetic board and chip protectivecoatings, embedded passives, laminating adhesives, capacitordielectrics, high frequency insulator/connectors, high voltageinsulators, high temperature wire coatings, conductive adhesives,reworkable adhesives, photosensitive adhesives and dielectric film,resistors, inductors, capacitors, antennas and printed circuit boardsubstrates. In optical applications uses include but are not limited tooptical films, ophthalmic lenses, wave guides, optical fiber,photosensitive optical film, specialty lenses, windows, high refractiveindex film, laser optics, color filters, optical adhesives, and opticalconnectors.

Some embodiments of the invention will now be described in detail in thefollowing examples. Some of the chemicals used in the Examples arelisted in Table II.

TABLE II Chemicals used in the examples. Chemical (purity) Source CAS #(Allyl)palladium(tricyclo- (a) hexylphosphine)chloride: Allylpalladiumchloride Strem, Newburyport, 12012-95-2 dimer (99%) MA 01950-4098Chlorobenzene Aldrich 108-90-7 Methylene Chloride (99+%) Aldrich 75-09-2Hexanes (98+) Aldrich 73513-42-5 Hexafluoroisopropanol 196314-61-1norbornene, 5-R—NB (R = CH₂C(CF₃)₂OH) Lithium tetrakis(pentafluoro-Boulder Scientific, phenyl)borate etherate Boulder, CO BSC-353 Q-5oxygen scavenger Engelhard, Iselin, NJ 08830 Silver hexafluoroanti-Aldrich 12005-82-2 monate (98%) Silver hexafluoro- Aldrich; Acros26042-63-7 phosphate (99.99%) Organics, Belgium Sodium tetrakis[3,5-Aldrich 79060-88-1 bis(trifluoro- methyl)phenyl]borate(98+)Tricyclohexyl- Strem 2622-14-2 phosphine (97%) (a) Prepared according tothe literature method of DiRenzo, G. M.; White, P. S.; Brookhart, M. J.Am. Chem. Soc. 1996, 118, 6225).; (b) Prepared according to theliterature method of Guzei, I. A., et al., S. F. Dalton Trans., 2003,715–722.

General procedures. The polymerization reactions of Examples 2, 9, 11,13, and 14 are carried out in a dry box under a nitrogen atmosphere. Thepolymerization reactions of Examples 1, 3–8, 10, and 12 are set upwithin a dry box under a nitrogen atmosphere. After the reaction is setup, the glass vessel is sealed, removed from the dry box, and heatedusing water bath in a fume hood.

Nitrogen is purified by passage through columns containing activatedmolecular sieves and Q-5 oxygen scavenger. Toluene is purified bypassage through columns of activated molecular sieves (4 Å)/alumina/O2remover (e.g., Q-5) and methylene chloride is purified by passagethrough columns of activated alumina. Lithiumtetrakis(pentafluorophenyl)borate etherate is purchased from BoulderScientific, allylpalladium chloride dimer (99%) andtricyclohexylphosphine (97%) are purchased from Strem, silverhexafluorophosphate (98%) is purchased from Acros, and all are usedwithout further purification. Methyl acrylate (99%) is purchased fromAldrich and purified by passage through columns of MEHQ inhibitorremover and activated molecular sieves (4 Å), and purged with nitrogenfor 0.5 hour. Norbornene (99%) is purchased from Micros and purifiedusing one of the following two methods: 1) It is dried with calciumhydride at 60° C. overnight, degassed by freeze-pump-thaw twice andvacuum transferred at 50° C. to a dry glass receiver; 2) It is dissolvedin a small amount of toluene to yield a clear colorless solution, whichis passed through a column of activated molecular sieves (4 Å) andpurged with nitrogen for 0.5 hour. The concentration of this toluenesolution of norbornene is determined by ¹H NMR analysis.Hexafluoroisopropanol norbornene and chlorobenzene are each sparged withnitrogen for 0.5 hours and then purified by passage over a columncontaining alumina and molecular sieves (3 Å).

Nuclear Magnetic Resonance (NMR) Spectroscopy. NMR spectra are recordedon Varian 600, Bruker DMX-400 or DRX-500 spectrometers at 23° C. unlessotherwise indicated. ¹H and ¹³C chemical shifts are reported vs. SiMe₄and are determined by reference to residual ¹H and ¹³C solvent signals.

Molecular Weight Determination using Gel Permeation Chromatography(GPC). Gel Permeation Chromatography, otherwise known as size exclusionchromatography, actually separates the members of a distribution ofpolymer chains according to their hydrodynamic size in solution ratherthan their molar mass. The system is then calibrated with standards ofknown molecular weight and composition to correlate elution time withmolecular weight. The techniques of GPC are discussed in detail inModern Size Exclusion Chromatography, W. W. Yau, J. J Kirkland, D. D.Bly; Wiley-Interscience, 1979, and in A Guide to MaterialsCharacterization and Chemical Analysis, J. P. Sibilia; VCH, 1988,p.81–84.

All samples are prepared at concentration 2 mg/mL in THF or chloroform(HPLC grade) and gently stirred to dissolve the polymer samplecompletely. All polymer solutions are filtered using 1 μm PTFE filter.GPC separation are performed using 2 PL gel Mixed B columns andevaporative light scattering detector (ELSD). Typical chromatographicconditions: 2 PL gel MIXED B columns, particle size 5 μm; eluent: THF orCHC13 (HPLC grade), 1.0 ml/min; injected volume of sample solution: 50μL; PS standards with molecular weight ranging from 580 to 2,560,000g/mol (0.5 mg/mL in THF or CHCl3) are used to construct calibrationcurve; ELS detection, (TN=40° C., TECH=80° C., Fnitrogen=1 L/min).

Liquid Chromatography—NMR. Typical LC-NMR experiment conditions: asample is dissolved in CDCl₃ to form a solution (ca. 1%) and filteredthrough a 0.2 micron filter. The polymer separation is carried out on aSUPLECOSIL reverse-phase C-18 column (25 cm×4.6 mm), with a flow rate of1 ml/min. The Evaporative Light Scattering detection (ELSD) and UVdetectors are employed with a solvent gradient of acetonitrile/water/THFfrom 95/5/0 to, 0/0/100 in 24 minutes. ¹H LC-NMR spectra are acquired ona Varian UNITY INOVA 600 MHz. NMR spectrometer.

Differential Scanning Calorimetry (DSC). Modulated Differential ScanningCalorimetry measurements are carried out on a Q-1000 Series DSC made byTA Instruments. Samples are run under an inert atmosphere of nitrogen ata flow rate of 25 mL/min. Samples are heated from −90° C. to +380° C. ata rate of 7° C./min with a modulation amplitude of 1° C. and a period of40 s

The following cationic metal-pair complexes are utilized in theexamples:

Precursor complex 1. (Reference: MacAdams, L. A.; Kim, W.-K.;Liable-Sands, L. M.; Guzei, I. A.; Rheingold, A. L.; Theopold, K. H.Organometallics 2002 21 952.)

Precursor complex 2. (Reference: DiRenzo, G. M.; White, P. S.;Brookhart, M. J. Am. Chem. Soc. 1996 118 6225)

EXAMPLE A Synthesis of Cationic Metal-Pair Complex 5

A 50 mL Schlenk is charged with precursor complex 1 (20 mmol). CH₂Cl₂(10 mL) is added to form a clear brown solution. A solution of potassiumtetrakis(pentafluorophenyl)borate (20 mmol) in CH₂Cl₂ (5 mL) is added bysyringe at 0° C. to form a brown solution with a white precipitate. Thereaction mixture is stirred at 0° C. for 15 min. The mixture is filteredto remove KCl, and the product is dried under vacuum to afford a brownsolid, which is purified by crystallization in CH₂Cl₂ (1 mL) at −80° C.The experiment should afford a brown solid(yield: 85%). NMR spectrashould reveal that the product is Catalyst 5.

EXAMPLE B Synthesis of Cationic Metal-Pair Complex 6

A 50 mL Schlenk is charged with precursor complex 1 (10 mmol). CH₂Cl₂(20 mL) is added to form a clear brown solution. A solution of potassiumtetrakis(pentafluorophenyl)borate (20 mmol) in CH₂Cl₂ (20 mL) is addedby syringe at 0° C. to form a brown solution with a white precipitate.The reaction mixture is stirred at 0° C. for 35 min. A solution ofprecursor complex 2 (20 mmol) in CH₂Cl₂ (20 mL) is added by syringe at0° C. to form a brown yellow solution. The reaction mixture is stirredat 0° C. for 25 min. The mixture is filtered to remove KCl, and theproduct is dried under vacuum to afford a brown solid, which is purifiedby crystallization in CH₂Cl₂ (2.5 mL) at −80° C. The experiment shouldafford a brown solid (yield: 75%). NMR spectra should reveal that theproduct is Catalyst 6.

EXAMPLE 1

Utilizing a cationic metal-pair complex to prepare a homopolymer ofnorbornene, according to the method of the present invention. A 100 mLserum bottle is charged with toluene (20 mL) and norbornene (1.13 g, 12mmol, pre-dissolved in toluene, 86 wt %) and sealed with a rubberseptum. A solution of Cationic metal-pair complex 1 (0.1 μmol) in CH₂Cl₂(1 mL) is added by syringe at 50° C. The reaction mixture is stirred at50° C. for 1 which is then cooled to ambient temperature and quenchedwith methanol (50 mL) to yield an off-white slurry. The solid isisolated by filtration, washed with fresh methanol (3×15 mL) and driedunder vacuum at 60° C. overnight, which should yield an off-white solid(0.95 g). NMR analysis should reveal that the product is polynorbornene.GPC analysis should reveal a unimodal pattern: Mw 1200000, Mn 1000000,Mw/Mn 1.2.

EXAMPLE 2

Utilizing a cationic metal-pair complex to prepare a homopolymer ofethylene, according to the method of the present invention. Toluene (3mL) is charged to the glass liner of a steel pressure vessel (8 mLcapacity) equipped with a mechanical stirrer. The pressure vessel issealed and heated to 50° C. Ethylene pressure (350 psig) is introduced.Cationic metal-pair complex 1 (8 μmol in 0.25 mL of methylene chloride)is injected to the pressure vessel using an oven dried gas tightsyringe. 0.75 mL of toluene is added via syringe to rinse the injectionport. The polymerization is allowed to proceed under these reactionconditions for 2 h. After this time, the reactor is vented and thecontents of the glass liner are added to methanol. After stirringovernight, the precipitated polymer is collected by vacuum filtrationand washed with methanol. The polymer is dried in a vacuum oven heatedto 60° C. overnight. The melting transitions measured by DifferentialScanning Calorimetry (DSC) should be about 130° C. and the heat offusion (ΔH_(f)) should be greater than 100 J/g.

EXAMPLE 3

Utilizing a cationic metal-pair complex to prepare a homopolymer ofmethyl acrylate, according to the method of the present invention. A 100mL serum bottle is charged with toluene (20 mL) and methyl acrylate (8.6g, 0.1 mol) and sealed with a rubber septum. A solution of Cationicmetal-pair complex 7 (10 μmol) in CH₂Cl₂ (1 mL) is added by syringe at50° C. The reaction mixture is stirred at 50° C. for 4 hours and thencooled to ambient temperature and quenched with methanol (100 mL). Theprecipitated polymer is isolated by filtration, washed with freshmethanol (3×25 mL) and dried under vacuum at 65° C. overnight, whichshould yield a white solid (1.2 g). NMR analysis should reveal that theproduct is poly(methyl acrylate). GPC analysis should reveal a unimodalpattern: Mw 100000, Mn 58000, Mw/Mn 1.7.

EXAMPLE 4

Utilizing a cationic metal-pair complex to prepare a homopolymer ofstyrene, according to the method of the present invention. A 100 mLserum bottle is charged with toluene (20 mL) and styrene (10.4 g, 0.1mol) and sealed with a rubber septum. A solution of Cationic metal-paircomplex 2 (10 μmol) in CH₂Cl₂ (1 ML) is added by syringe at 50° C. Thereaction mixture is stirred at 50° C. for 4 hours and then cooled toambient temperature and quenched with methanol (100 mL). Theprecipitated polymer is isolated by filtration, washed with freshmethanol (3×25 mL) and dried under vacuum at 65° C. overnight, whichshould yield a white solid (5 g). NMR analysis should reveal that theproduct is polystyrene. GPC analysis should reveal a unimodal pattern:Mw 250000, Mn 125000, Mw/Mn 2.0.

EXAMPLE 5

Utilizing a cationic metal-pair complex to prepare a homopolymer ofvinyl acetate, according to the method of the present invention. A 100mL serum bottle is charged with toluene (20 mL) and vinyl acetate (8.6g, 0.1 mol) and sealed with a rubber septum. A solution of Cationicmetal-pair complex 2 (10 μmol) in CH₂Cl₂ (1 mL) is added by syringe at50° C. The reaction mixture is stirred at 50° C. for 4 hours and thencooled to ambient temperature and quenched with methanol (100 mL). Theprecipitated polymer is isolated by filtration, washed with freshmethanol (3×25 mL) and dried under vacuum at 65° C. overnight, whichshould yield a white solid (2.0 g). NMR analysis should reveal that theproduct is poly(vinyl acetate). GPC analysis should reveal a unimodalpattern: Mw 170000, Mn 86000, Mw/Mn 2.0.

EXAMPLE 6

Utilizing a cationic metal-pair complex to prepare a homopolymer ofvinyl chloride, according to the method of the present invention. AFischer-Porter reactor is charged with toluene (10 mL). Vinyl chloride(89 mmol, measured by a 800-mL glass bulb) is added by condensation at−196° C. The reactor is gradually warmed to −78° C. and Cationicmetal-pair complex 3 (0.6 μmol) in CH₂Cl₂ (1 mL) is added by a syringethrough a rubber septum. The reactor is sealed and gradually warmed to55° C., at which temperature the reaction mixture is vigorously stirred.6 hours later, the reactor is cooled to ambient temperature an excesspressure is released before the reaction mixture is poured into a beakercontaining acidified methanol (1 v/v %, 250 mL) to yield a white slurry.The solid is collected by filtration, washed with fresh methanol (3×15mL) and dried under vacuum at 60° C. for 18 hours, which should yield awhite solid (4.8 g). NMR analysis should reveal that the product ispoly(vinyl chloride). GPC analysis should reveal a unimodal pattern: Mw220000, Mn 200000, Mw/Mn 1.1.

EXAMPLE 7

Utilizing a cationic metal-pair complex to prepare a homopolymer ofmethyl vinyl ether, according to the method of the present invention. A100 mL serum bottle is charged with toluene (20 mL) and methyl vinylether (5.8 g, 0.1 mol, pre-dissolved in toluene, 74 wt %) and sealedwith a rubber septum. A solution of Cationic metal-pair complex 4 (0.25μmol) in CH₂Cl₂ (1 mL) is added by syringe at 50° C. The reactionmixture is stirred at 50° C. for 4 hours, which is then cooled toambient temperature and quenched with methanol (100 mL) to yield a whiteslurry. The solid is isolated by filtration, washed with fresh methanol(3×25 mL) and dried under vacuum at 65° C. overnight, which should yielda white solid (5.1 g). NMR analysis should reveal that the product ispoly(methyl vinyl ether). GPC analysis should reveal a unimodal pattern:Mw 140000, Mn 100000, Mw/Mn 1.4.

EXAMPLE 8

Utilizing a cationic metal-pair complex to prepare a copolymer of5-R-norbornene (R=CH₂C(CF₃)₂(OH)) and tert-butyl acrylate, according tothe method of the present invention. The 100 mL serum bottle is chargedwith toluene (25 mL), 5-R-norbornene (13.7 g, 50 mmol), tert-butylacrylate (6.4 g, 50 mmol), and sealed under N₂ with a rubber septum. Asolution of Cationic metal-pair complex 4 (0.15 μmol) in CH₂Cl₂ is addedby syringe at 50° C. The reaction mixture is stirred at 50° C. 3.5 hourslater, the reaction mixture is cooled to ambient temperature andquenched with hexane (250 mL) to form a white slurry immediately. Thesolid is isolated by filtration and all volatile species are removedunder vacuum (0.5 mmHg) at 60° C. overnight. The remaining solid is thenre-dissolved in CHCl₃ and the solution is passed through a column of ionexchange resin to remove catalyst residues. The purified solution iscollected and CHCl₃ is removed under vacuum at 50° C. overnight, whichshould yield a white powder (14.2 g). ¹³C NMR experiment should revealthat the product has a molar ratio of 55 (5-R-norbornene): 45(tert-butyl acrylate). GPC analysis should reveal a unimodal pattern: Mw25000, Mn 20000, Mw/Mn 1.25.

EXAMPLE 9

Utilizing a cationic metal-pair complex to prepare a copolymer ofethylene and methyl acrylate, according to the method of the presentinvention. Methyl acrylate (1 mL) and toluene (3 mL) are charged to theglass liner of a steel pressure vessel (8 mL capacity) equipped with amechanical stirrer. The pressure vessel is sealed and heated to 50° C.Ethylene pressure (350 psig) is introduced. Cationic metal-pair complex3 (8 μmol in 0.25 mL of methylene chloride) is injected to the pressurevessel using an oven dried gas tight syringe. 0.75 mL of toluene isadded via syringe to rinse the injection port. The polymerization isallowed to proceed under these reaction conditions for 4 h. After thistime, the reactor is vented and the contents of the glass liner areadded to methanol. After stirring overnight, the precipitated polymer iscollected by vacuum filtration and washed with methanol. The polymer isdried in a vacuum oven heated to 60° C. overnight. ¹H NMR should revealthat the product is a copolymer with a molar ratio of 80 (ethylene):20(methyl acrylate). GPC analysis should reveal a unimodal pattern: Mw80000, Mn 50500, Mw/Mn 1.6.

EXAMPLE 10

Utilizing a cationic metal-pair complex to prepare a copolymer ofnorbornene and methyl acrylate, according to the method of the presentinvention. A 100 mL serum bottle is charged with toluene (20 mL),norbornene (1.70 g, 18 mmol, pre-dissolved in toluene, 86 wt %), methylacrylate (1.0 g, 12 mmol) and sealed with a rubber septum. A solution ofCationic metal-pair complex 5 (0.2 μmol) in CH₂Cl₂ is added by syringeat 50° C. The reaction mixture is vigorously stirred at 50° C. 5 hourslater, the reaction mixture is cooled to ambient temperature andquenched with methanol (200 mL) to form a pale yellow slurryinstantaneously. The solid is isolated by filtration, washed with freshmethanol (3×25 mL), and dried under vacuum at 60° C. overnight, whichshould yield a pale yellow solid (2.4 g). NMR analysis should revealthat the product has a molar ratio of 72 (norbornene): 28 (methylacrylate). GPC analysis should reveal a unimodal pattern: Mw 60000, Mn40000, Mw/Mn 1.25.

EXAMPLE 11

Utilizing a cationic metal-pair complex to prepare a copolymer ofethylene and norbornene, according to the method of the presentinvention. Norbornene (2 mL of a 79 wt % solution in toluene) andtoluene (2 mL) are charged to the glass liner of a steel pressure vessel(8 mL capacity) equipped with a mechanical stirrer. The pressure vesselis sealed and heated to 50° C. Ethylene pressure (350 psig) isintroduced. Cationic metal-pair complex 7 (8 μmol in 0.25 mL ofmethylene chloride) is injected to the pressure vessel using an ovendried gas tight syringe. 0.75 mL of toluene is added via syringe torinse the injection port. The polymerization is allowed to proceed underthese reaction conditions for 2 h. After this time, the reactor isvented and the contents of the glass liner are added to methanol. Afterstirring overnight, the precipitated polymer is collected by vacuumfiltration and washed with methanol. The polymer is dried in a vacuumoven heated to 60° C. overnight. ¹H NMR should reveal that the productis a copolymer with a molar ratio of 55 (ethylene):45 (norbornene). GPCanalysis should reveal a unimodal pattern: Mw 150000, Mn 80000, Mw/Mn1.9.

EXAMPLE 12

Utilizing a catalytic cationic metal-pair complex to prepare aterpolymer of norbornene, 1-octene and methyl acrylate, according to themethod of the present invention. A 100-mL serum bottle is charged withnorbornene (12 mmol, pre-dissolved in toluene, 79wt %), methyl acrylate(12 mmol), 1-octene (30 mmol) and toluene (20 mL), and sealed with arubber septum. A solution of Cationic metal-pair complex 6 (0.34 μmol)in CH₂Cl₂ is added by syringe at 50° C. The reaction mixture is stirredat 50° C. 4 hours later, the reaction mixture is cooled to ambienttemperature and methanol (250 mL). The solid is isolated by filtration,washed with fresh methanol (3×25 mL) and dried under vacuum at 70 deg C.overnight, which should yield a white solid (2.5 g). NMR analysis shouldreveal that the product has a molar ratio of 15 (norbornene):30(1-octene):55 (methyl acrylate). GPC experiment should reveal a unimodalpattern: Mw 70000, Mn 43750, Mw/Mn 1.6.

EXAMPLE 13

Utilizing a cationic metal-pair complex to prepare a copolymer ofethylene and methyl methacrylate, according to the method of the presentinvention. Methyl methacrylate (1 mL) and toluene (2 mL) are charged tothe glass liner of a steel pressure vessel (8 mL capacity) equipped witha mechanical stirrer. The pressure vessel is sealed and heated to 50° C.Ethylene pressure (350 psig) is introduced. Cationic metal-pair complex5 (8 μmol in 0.25 mL of methylene chloride) is injected to the pressurevessel using an oven dried gas tight syringe. 0.75 mL of toluene isadded via syringe to rinse the injection port. The polymerization isallowed to proceed under these reaction conditions for 4 h. After thistime, the reactor is vented and the contents of the glass liner areadded to methanol. After stirring overnight, the precipitated polymer iscollected by vacuum filtration and washed with methanol. The polymer isdried in a vacuum oven heated to 60° C. overnight. ¹H NMR should revealthat the product is a copolymer with a molar ratio of 90 (ethylene):10(methyl methacrylate). GPC analysis should reveal a unimodal pattern: Mw25000, Mn 15000, Mw/Mn 1.7.

EXAMPLE 14

Utilizing a cationic metal-pair complex to prepare a copolymer ofethylene and styrene, according to the method of the present invention.Styrene (1 mL) and toluene (2 mL) are charged to the glass liner of asteel pressure vessel (8 mL capacity) equipped with a mechanicalstirrer. The pressure vessel is sealed and heated to 50° C. Ethylenepressure (350 psig) is introduced. Cationic metal-pair complex 6 (8 μmolin 0.25 mL of methylene chloride) is injected to the pressure vesselusing an oven dried gas tight syringe. 0.75 mL of toluene is added viasyringe to rinse the injection port. The polymerization is allowed toproceed under these reaction conditions for 4 h. After this time, thereactor is vented and the contents of the glass liner are added tomethanol. After stirring overnight, the precipitated polymer iscollected by vacuum filtration and washed with methanol. The polymer isdried in a vacuum oven heated to 60° C. overnight. ¹H NMR should revealthat the product is a copolymer with a molar ratio of 60 (ethylene):40(styrene). GPC analysis should reveal a unimodal pattern: Mw 95000, Mn60000, Mw/Mn 1.6.

1. A catalytic composition comprising at least one cationic metal-paircomplex, wherein: said cationic metal-pair complex comprises at leastone metal atom pair, said pair comprising a first metal atom, M¹, and asecond metal atom, M²; said first metal atom and said second metal atomof said pair have a through-space internuclear distance of at least 1.5Angstroms and no more than 20 Angstroms; and said cationic metal-paircomplex is a complex according to formula I,

wherein: M¹ represents a first metal atom selected from iron, cobalt,ruthenium, rhodium, chromium, and manganese; L¹ represents a set offirst ligands; L2 represents a set of second ligands; L3 represents aset of third ligands; R1 represents a set of first anionic hydrocarbylcontaining radicals; R2 represents a set of second anionic hydrocarbylcontaining radicals; S1 represents a set of first labile ligands; S2represents a set of second labile ligands; A1–A8 each represent a set ofcoordination bonds; WCA represents a weakly coordinating anion; a, b, h,k, m, and p are each selected from 0 and 1; α, β, and c each equal 1; d,r, and t are each selected from 0, 1, 2, 3, and 4; f is selected from 1,2, 3, 4, and 5; 1≦m+p≦2; the sum d+f+r+t=5; and sum e+g+s+u=4, 5, or 6;and wherein: when the sum e+g+s+u=4, M² represents a second metal atomselected from nickel, palladium, copper, iron, cobalt, rhodium,chromium, and manganese; e, s, and u are each selected from 0, 1, 2, and3; g is selected from 1, 2, 3, and 4; 0≦d+e≦6; 1≦r+s≦6; 0≦t+u≦6; and2≦f+g≦8; when the sum e+g+s+u=5, M² represents a second metal atomselected from iron, cobalt, ruthenium, rhodium, chromium, and manganese;e, s, and u are each selected from 0, 1, 2, 3, and 4; g is selected from1, 2, 3, 4, and 5; 0≦d+e≦7; 1≦r+s≦7; 0≦t+u≦7; and 2f+g≦9; or when thesum e+g+s+u=6, M² represents a second metal atom selected from copper,iron, cobalt, ruthenium, rhodium, chromium, and manganese; e, s, and uare each selected from 0, 1, 2, 3, 4, and 5; g is selected from 1, 2, 3,4, 5, and 6; 0≦d+e≦8; 1≦r+s≦8; 0≦t+u≦8; and 2≦f+g≦10.
 2. The catalyticcomposition of claim 1, wherein said first metal atom and said secondmetal atom of said pair have a through-space internuclear distance of atleast 2 Angstroms and no more than 10 Angstroms.
 3. The catalyticcomposition of claim 1, wherein at least one of said first anionichydrocarbyl radicals and said second anionic hydrocarbyl radicals is anaddition polymer.
 4. A method for preparing the catalytic composition ofclaim 1, comprising: (i) providing a full-(metal pair) precursor complexaccording to said formula II

 wherein: M¹ represents a first metal atom selected from iron, cobalt,ruthenium, rhodium, chromium, and manganese; L¹ represents a set offirst ligands; L²represents a set of second ligands; L³ represents a setof third ligands; R¹ represents a set of first anionic hydrocarbylcontaining radicals; R² represents a set of second anionic hydrocarbylcontaining radicals; S¹ represents a set of first labile ligands; S²represents a set of second labile ligands; A¹–A¹⁰ each represents a setof coordination bonds; Y represents a leaving group; d+f+r+t+x=5; andthe sum e+g+s+u+y=4, 5, or 6; (ii) combining said full-(metal pair)precursor complex with at least one activator component; (iii) removingsaid leaving group Y from said full-(metal pair) precursor complex; and(iv) replacing said leaving group Y with at least one replacementmoiety; wherein for said full-(metal pair) precursor complex α, β, and ceach equal 1; a, b, h, k, m, p, x, and y are each selected from 0 and 1;d, r, and t are each selected from 0, 1, 2, 3, and 4; f is selected from1, 2, 3, 4, and 5; 1≦m+p≦2; and 1≦x+y≦2; wherein: when the sume+g+s+u+y=4, M² represents a second metal atom selected from nickel,palladium, copper, iron, cobalt, rhodium, chromium, and manganese; e, s,and u are selected from 0, 1, 2, and 3; g is selected from 1, 2, 3, and4; 0≦d+e≦5; 1≦r+s≦6; 0≦t+u≦5; and 2≦f+g≦7; when the sum e+g+s+u+y=5, M²represents a second metal atom selected from iron, cobalt, ruthenium,rhodium, chromium, and manganese; e, s, and u are selected from 0, 1, 2,3, and 4; g is selected from 1, 2, 3, 4, 5, and 6; 0≦d+e≦7; 1≦r+s≦8;0≦t+u≦7; and 2≦f+g≦9.
 5. A method for preparing the catalyticcomposition of claim 1, comprising: (i) providing a first semi-(metalpair) precursor complex and a second semi-(metal pair) precursor complexboth according to formula II

 wherein: M¹ represents a first metal atom selected from iron, cobalt,ruthernium,rhodium, chromium, and manganese; L¹ represents a set offirst ligands; L²represents a set of second ligands; L³ represents a setof third ligands; R¹ represents a set of first anionic hydrocarbylcontaining radicals; R² represents a set of second anionic hydrocarbylcontaining radicals; S¹ represents a set of first labile ligands; S²represents a set of second labile ligands; A¹–A¹⁰ each represents a setof coordination bonds; and Y represents a leaving group; (ii) combiningsaid first semi-(metal pair) precursor complex with at least oneactivator component; (iii) removing said leaving group Y from said firstsemi-(metal pair) precursor complex; and (iv) replacing said leavinggroup Y with said second semi-(metal pair) precursor complex; whereinfor said first semi-(metal pair) precursor complex α and x each equal 1;β, b, c, k, p, e, f, g, s, u, and y each equal 0; a, h, and m are eachselected from 0 and 1; d, r, and t are each selected from 0, 1, 2, 3,and 4; and the sum d+f+r+t+x=5; and wherein for said second semi-(metalpair) precursor complex β equals 1; α, a, c, h, m, d, f, g, r, t, x, andy each equal 0; b, k, and p are each selected from 0 and 1; and the sume+g+s+u+y=4, 5 and 6; and wherein: when the sum e+g+s+u+y=4, M²represents a second metal atom selected from nickel, palladium, copper,iron, cobalt, rhodium, chromium, and manganese; e is selected from 0, 1,2, 3, and 4; and s and u are each selected from 0, 1, 2, and 3; when thesum e+g+s+u+y=5, M² represents a second metal atom selected from iron,cobalt, ruthenium, rhodium, chromium, and manganese; e is selected from0, 1, 2, 3, 4, and 5; and s and u are each selected from 0, 1, 2, 3, and4; or when the sum e+g+s+u+y=6 M² represents a second metal atomselected from copper, iron, cobalt, ruthenium, rhodium, chromium, andmanganese; e is selected from 0, 1, 2, 3, 4, 5, and 6; and s and u areeach selected from 0, 1, 3, 4, and 5; and wherein the sum of m of saidfirst semi-(metal pair) precursor complex+p of said second semi-(metalpair) precursor complex is selected from 1 or
 2. 6. A method forpreparing the catalytic composition of claim 1, comprising: (i)providing a first semi-(metal pair) precursor complex and a secondsemi-(metal pair) precursor complex both according to formula II

 wherein: M¹ represents a first metal atom selected from iron, cobalt,ruthenium, rhodium, chromium, and manganese; L¹ represents a set offirst ligands; L² represents a set of second ligands; L³ represents aset of third ligands; R¹ represents a set of first anionic hydrocarbylcontaining radicals; R² represents a set of second anionic hydrocarbylcontaining radicals; S¹ represents a set of first labile ligands; S²represents a set of second labile ligands; A¹–A¹⁰ each represents a setof coordination bonds; and Y represents a leaving group; (ii) combiningsaid first semi-(metal pair) precursor complex with at least oneactivator component; (iii) removing said leaving group Y from said firstsemi-(metal pair) precursor complex; and (iv) replacing said leavinggroup Y with said second semi-(metal pair) precursor complex; whereinfor said first semi-(metal pair) precursor complex β and y each equal 1;α, a, c, h, m, d, f, g, r, t, and x each equal 0; b, k, and p are eachselected from 0 and 1; and the sum e+g+s+u+y=4, 5 or 6; and wherein:when the sum e+g+s+u+y=4, M² represents a second metal atom selectedfrom nickel, palladium, copper, iron, cobalt, rhodium, chromium, andmanganese; and e, s and u are each selected from 0, 1, 2, and 3; whenthe sum e+g+s+u+y=5, M² represents a second metal atom selected fromiron, cobalt, ruthenium, rhodium, chromium, and manganese; and e, s andu are each selected from 0, 1, 2, 3, and 4; or when the sum e+g+s+u+y=6M² represents a second metal atom selected from copper, iron, cobalt,ruthenium, rhodium, chromium, and manganese; and e, s and u are eachselected from 0, 1, 2, 3, 4, and 5; and wherein for said secondsemi-(metal pair) precursor complex α equals 1; β, b, c, k, p, e, f, g,s, u, x, and y each equal 0; a, h, and m are each selected from 0 and 1;d is selected from 0, 1, 2, 3, 4, and 5; r and t are each selected from0, 1, 2, 3, and 4; and the sum d+f+r+t+x=5; and wherein the sum of m ofsaid first semi-(metal pair) precursor complex+p of said secondsemi-(metal pair) precursor complex is selected from 1 or
 2. 7. A methodfor preparing at least one addition polymer comprising: (a) combining:(i) a catalytic composition according to claim 1; and (ii) at least oneethylenically unsaturated monomer; and (b) polymerizing said at leastone ethylenically unsaturated monomer in the presence of said catalyticcomposition to form said addition polymer.
 8. The method of claim 7,wherein said at least one addition polymer is selected from poly[(polarolefin)-(non-polar olefin)], poly(polar olefin), poly(non-polar olefin),and combinations thereof, wherein said at least one said ethylenicallyunsaturated monomer is selected from at least one polar olefinicmonomer, at least one non-polar olefinic monomer, and combinationsthereof.
 9. The method of claim 8, wherein said poly[(polarolefin)-(non-polar olefin)] has a combined molar percentage of polarolefinic monomers and non-polar olefinic monomers present, aspolymerized units, of at least 70 mole-% to 100 mole-%, based upon thetotal moles of all polar olefinic monomers and non-polar olefinicmonomers present, as polymerized units, in said at least one additionpolymer.
 10. The method of claim 7, wherein said addition polymercomprises, as polymerized units, at least one (meth)acrylate monomer,wherein said (meth)acrylate monomers have a molar ratio to all saidethylenically unsaturated monomers, present as polymerized units, of atleast 0.05:99.95 to 100:0.
 11. The method of claim 7, wherein saidaddition polymer comprises, as polymerized units, at least one cyclicolefin monomer, wherein said cyclic olefin monomers have a molar ratioto all said ethylenically unsaturated monomers, present as polymerizedunits, of at least 0.05:99.95 to 100:0.